Phenyl(oxy/thio)alkanol Derivatives

ABSTRACT

The present invention relates to novel phenyl(oxy/thio)alkanol derivatives, to processes for preparing these compounds, to compositions comprising these compounds and to their use as biologically active compounds, in particular for controlling harmful microorganisms in crop protection and in the protection of materials and as plant growth regulators.

The present invention relates to novel phenyl(oxy/thio)alkanolderivatives, to processes for preparing these compounds, to compositionscomprising these compounds and to their use as biologically activecompounds, in particular for controlling harmful microorganisms in cropprotection and in the protection of materials and as plant growthregulators.

It is already known that certain phenyl(oxy/thio)alkanol derivatives canbe used in crop protection as fungicides and/or growth regulators (cf.DE-A 39 05 317, JP-A 58-124772, EP-A 0 298 332, EP-A 0 028 755, EP-A 0061 835, EP-A 0 040 345, EP-A 0 001 399, EP-A 0 793 657 and EP-A 0 594963).

Since the ecological and economical demands made on modern activecompounds, for example fungicides, are increasing constantly, forexample with respect to activity spectrum, toxicity, selectivity,application rate, formation of residues and favourable manufacture, andthere can furthermore be problems, for example, with resistances, thereis a constant need to develop novel fungicides which, at least in someareas, have advantages over the known ones.

This invention, accordingly, provides novel phenyl(oxy/thio)alkanolderivatives of the formula (I)

in which

-   X represents 5-pyrimidinyl, 1H-1,2,4-triazol-1-ylmethyl,    3-pyridinyl, 1H-1,3-imidazol-1-ylmethyl or    2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl,-   Y represents O, S, SO, SO₂ or CH₂,-   Z represents bromine or iodine,-   R represents tert-butyl, isopropyl, 1-halocyclopropyl,    1-(C₁-C₄-alkyl)cyclopropyl, 1-(C₁-C₄-alkoxy)-cyclopropyl or    1-(C₁-C₄-alkylthio)cyclopropyl,    and the agrochemically active salts thereof,    except for the compounds-   1-(4-bromophenoxy)-3,3-dimethyl-2-(pyridin-3-yl)butan-2-ol-   1-(4-bromophenylthio)-3,3-dimethyl-2-(pyridin-3-yl)butan-2-ol-   1-(4-bromophenylthio)-3-methyl-2-(pyridin-3-yl)butan-2-ol-   2-(4-bromophenoxy)-1-(1-chlorocyclopropyl)-1-(pyridin-3-yl)ethanol-   1-(4-bromophenoxy)-3,3-dimethyl-2-(1H-1,2,4-triazol-1-ylmethyl)butan-2-ol-   1-(4-bromophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol-   4-(4-bromophenyl)-2-(1-methylcyclopropyl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol-   4-(4-bromophenyl)-2-(1-chlorocyclopropyl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol.

The salts obtainable in this manner also have fungicidal and/or plantgrowth regulatory properties.

The formula (I) provides a general definition of thephenyl(oxy/thio)alkanol derivatives which can be used according to theinvention. Preferred radical definitions for the formulae shown aboveand below are given below. These definitions apply to the end productsof the formula (I) and likewise to all intermediates (see also belowunder “Illustration of the processes and intermediates”).

-   X preferably represents 5-pyrimidinyl, 1H-1,2,4-triazol-1-ylmethyl,    3-pyridinyl or 2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.-   X particularly preferably represents 5-pyrimidinyl.-   X also particularly preferably represents    1H-1,2,4-triazol-1-ylmethyl.-   X also particularly preferably represents    2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.-   X very particularly preferably represents 5-pyrimidinyl.-   X also very particularly preferably represents    1H-1,2,4-triazol-1-ylmethyl.-   Y preferably represents O, S or CH₂.-   Y particularly preferably represents O or CH₂.-   Y very particularly preferably represents O.-   Z preferably represents bromine.-   Z also preferably represents iodine.-   Z particularly preferably represents bromine which is located in    position 4.-   Z also particularly preferably represents bromine which is located    in position 3.-   Z also particularly preferably represents bromine which is located    in position 2.-   Z also particularly preferably represents iodine which is located in    position 4.-   Z also particularly preferably represents iodine which is located in    position 3.-   Z also particularly preferably represents iodine which is located in    position 2.-   R preferably represents tert-butyl, isopropyl, 1-chlorocyclopropyl,    1-fluorocyclopropyl, 1-methylcyclopropyl, 1-methoxycyclopropyl or    1-methylthiocyclopropyl.-   R particularly preferably represents tert-butyl, isopropyl,    1-chlorocyclopropyl, 1-fluorocyclopropyl or 1-methylcyclopropyl.-   R very particularly preferably represents tert-butyl.-   R also very particularly preferably represents isopropyl.-   R also very particularly preferably represents 1-chlorocyclopropyl.-   R also very particularly preferably represents 1-fluorocyclopropyl.-   R also very particularly preferably represents 1-methylcyclopropyl.

A further embodiment of the present invention relates to compounds ofthe formula (I-a)

in which Y, Z and R have the meanings given above.

A further embodiment of the present invention relates to compounds ofthe formula (I-b)

in which Y, Z and R have the meanings given above.

A further embodiment of the present invention relates to compounds ofthe formula (I-c)

in which Y, Z and R have the meanings given above.

In this formula (I-c), Z preferably represents iodine.

A further embodiment of the present invention relates to compounds ofthe formula (I-d)

in which Y, Z and R have the meanings given above.

In this formula (I-d), Z preferably represents iodine.

A further embodiment of the present invention relates to compounds ofthe formula (I-e)

in which Y, Z and R have the meanings given above.

A further embodiment of the present invention relates to compounds ofthe formula (I-f)

in which Y, Z and R have the meanings given above.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine and R represents tert-butyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine and R represents isopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine and R represents1-chlorocyclopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine and R represents1-fluorocyclopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine and R represents1-methylcyclopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine and R represents tert-butyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine and R represents isopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine and R represents1-chlorocyclopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine and R represents1-fluorocyclopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine and R represents1-methylcyclopropyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents tert-butyl and Xrepresents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents tert-butyl and Xrepresents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents tert-butyl and Xrepresents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents tert-butyl and Xrepresents 2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents isopropyl and Xrepresents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents isopropyl and Xrepresents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents isopropyl and Xrepresents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents isopropyl and Xrepresents 2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-chlorocyclopropyl and X represents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-chlorocyclopropyl and X represents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-chlorocyclopropyl and X represents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-chlorocyclopropyl and X represents2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-fluorocyclopropyl and X represents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-fluorocyclopropyl and X represents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-fluorocyclopropyl and X represents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-fluorocyclopropyl and X represents2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents tert-butyl and Xrepresents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents tert-butyl and Xrepresents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents tert-butyl and Xrepresents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents tert-butyl and Xrepresents 2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents isopropyl and Xrepresents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents isopropyl and Xrepresents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents isopropyl and Xrepresents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents isopropyl and Xrepresents 2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-chlorocyclopropyl and X represents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-chlorocyclopropyl and X represents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-chlorocyclopropyl and X represents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-chlorocyclopropyl and X represents2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-fluorocyclopropyl and X represents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-fluorocyclopropyl and X represents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-fluorocyclopropyl and X represents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents iodine, R represents1-fluorocyclopropyl and X represents2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-methylcyclopropyl and X represents 5-pyrimidinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-methylcyclopropyl and X represents 1H-1,2,4-triazol-1-ylmethyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-methylcyclopropyl and X represents 3-pyridinyl.

A further embodiment of the present invention are compounds of theformula (I) in which Z represents bromine, R represents1-methylcyclopropyl and X represents2,4-dihydro-3H-1,2,4-triazole-3-thion-1-yl-methyl.

The radical definitions and explanations stated above in general orstated in preferred ranges can, however, also be combined as desiredwith one another, that is to say between the respective ranges andpreferred ranges. They apply both to the end products and,correspondingly, to precursors and intermediates. Moreover, individualdefinitions may not apply.

Preference is given to compounds of the formula (I) in which allradicals have the preferred meanings mentioned above.

Particular preference is given to compounds of the formula (I) in whichall radicals have the particularly preferred meanings mentioned above.

Illustration of the Processes and Intermediates

The phenyl(oxy/thio)alkanol derivatives of the formula (I) can beprepared by various routes. Initially, the feasable processes are shownschematically below. Unless indicated otherwise, the radicals given havethe meanings given above.

Preferred radical definitions for the formulae and schemes shown aboveand below have already been given above. These definitions apply notonly to the end products of the formula (I) but likewise to allintermediates.

Process A

The oxirane derivatives of the formula (II) required as startingmaterials for carrying out the process A according to the invention arenovel, except for the compound2-[2-(4-bromophenyl)ethyl]-2-(1-methylcyclopropyl)oxirane. They can beprepared by known processes from the phenyloxy(thio)ketones of theformula (VI) (cf. EP-A 0 040 345).

The 1,2,4-triazole and the 1,3-imidazole of the formula (III) are known.

The process A according to the invention is carried out in the presenceof a diluent and, if appropriate, in the presence of a base. Ifappropriate, an acid or a metal salt is then added to the compound ofthe formula (I-g) obtained (see below).

Suitable diluents for the reaction according to the invention are allorganic solvents which are inert. These preferably include alcohols,such as, for example, ethanol and methoxyethanol; ketones, such as, forexample, 2-butanone; nitriles, such as, for example, acetonitrile;esters, such as, for example, ethyl acetate; ethers, such as, forexample, dioxane; aromatic hydrocarbons, such as, for example, benzeneand toluene; or amides, such as, for example, dimethylformamide.

Suitable bases for the reaction according to the invention are allorganic and inorganic bases which can customarily be used. Thesepreferably include alkali metal carbonates, such as, for example, sodiumcarbonate or potassium carbonate; alkali metal hydroxides, such as, forexample, sodium hydroxide; alkali metal alkoxides, such as, for example,sodium methoxide and potassium methoxide and sodium ethoxide andpotassium ethoxide; alkali metal hydrides, such as, for example, sodiumhydride; and also lower tertiary alkylamines, cycloalkylamines andaralkylamines, such as, in particular, triethylamine.

When carrying out the process according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between 0° C. and 200° C.,preferably between 60° C. and 150° C.

If appropriate, the reaction according to the invention can be carriedout under elevated pressure. In general, the reaction is carried outbetween 1 and 50 bar, preferably between 1 and 25 bar.

When carrying out the process A according to the invention, preferablyfrom 1 to 2 mol of 1,2,4-triazole or 1,3-imidazole of the formula (III)and, if appropriate, from 1 to 2 mol of base are employed per mole ofoxirane of the general formula (II). The isolation of the end productsis carried out in a generally customary manner.

Process B

Some of the oxirane derivatives of the formula (IV) required as startingmaterials for carrying out the process B according to the invention arenovel. They can be prepared by known processes from the correspondingtriazolylketones (cf. DE-A 31 11 238, EP-A 0 157 712).

Oxirane derivatives of the formula (IV-a)

in which

-   R^(a) represents isopropyl, 1-halocyclopropyl,    1-(C₁-C₄-alkyl)cyclopropyl, 1-(C₁-C₄-alkoxy)-cyclopropyl or    1-(C₁-C₄-alkylthio)cyclopropyl,-   A represents CH or N are novel.-   R^(a) preferably represents isopropyl, 1-chlorocyclopropyl,    1-methylcyclopropyl, 1-methoxy-cyclopropyl or    1-methylthiocyclopropyl.-   R^(a) particularly preferably represents isopropyl,    1-chlorocyclopropyl or 1-methylcyclopropyl.-   R^(a) very particularly preferably represents isopropyl.

Oxirane derivatives of the formula (IV-b)

in whichR has the meanings given above andA represents CH or N,where R does not represent tert-butyl if A represents CH are likewisenovel.

R preferably, particularly preferably and very particularly preferablyhas the meanings given above, where in each case R does not representtert-butyl if A represents CH.

The (thio)phenols of the formula (V) are known.

The process B according to the invention is carried out in the presenceof a diluent and, if appropriate, in the presence of a base. Ifappropriate, an acid or a metal salt is then added to the compound ofthe formula (I-h) obtained (see below).

Suitable diluents for the reaction according to the invention are allorganic solvents which are inert. These preferably include alcohols,such as, for example, ethanol and methoxyethanol; ketones, such as, forexample, 2-butanone; nitriles, such as, for example, acetonitrile;esters, such as, for example, ethyl acetate; ethers, such as, forexample, dioxane; aromatic hydrocarbons, such as, for example, benzeneand toluene; or amides, such as, for example, dimethylformamide.

Suitable bases for the reaction according to the invention are allorganic and inorganic bases which can customarily be used. Thesepreferably include alkali metal carbonates, such as, for example, sodiumcarbonate or potassium carbonate; alkali metal hydroxides, such as, forexample, sodium hydroxide; alkali metal alkoxides, such as, for example,sodium methoxide and potassium methoxide and sodium ethoxide andpotassium ethoxide; alkali metal hydrides, such as, for example, sodiumhydride; and also lower tertiary alkylamines, cycloalkylamines andaralkylamines, such as, in particular, triethylamine. Particularpreference is given to using sodium hydride.

When carrying out the process according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between 0° C. and 200° C.,preferably between 60° C. and 150° C.

If appropriate, the reaction according to the invention can be carriedout under elevated pressure. In general, the reaction is carried outbetween 1 and 50 bar, preferably between 1 and 25 bar.

When carrying out the process B according to the invention, preferablyfrom 1 to 2 mol of (thio)phenol of the formula (V) and, if appropriate,from 1 to 2 mol of base are employed per mole of oxirane of the generalformula (IV). The isolation of the end products is carried out in agenerally customary manner.

Process C

The phenyl(oxy/thio)ketones of the formula (VI) where Y does notrepresent O or CH₂ if Z represents bromine required as startingmaterials for carrying out the process C according to the invention arenovel. They can be prepared in a known manner (cf. EP-A 0 040 345, EP-A0 001 399).

The halides of the formula (VII) are known. In formula (VII), Hal ispreferably chlorine or bromine.

The process C according to the invention is carried out in the presenceof a diluent and in the presence of an organic alkali metal compound. Ifappropriate, an acid or a metal salt is then added to the compound ofthe formula (I-i) obtained (see below).

Preferred diluents for the reaction according to the invention are inertorganic solvents. These preferably include those having a low freezingpoint, such as, in particular, ethers, such as diethyl ether ortetrahydrofuran. Preference is given to working with mixtures of thesetwo ethers.

Preferred organic alkali metal compounds used for the reaction accordingto the invention are alkali metal alkyls, such as, in particular,n-butyllithium; however, it is also possible to use alkali metal aryls,such as phenyllithium.

In the process according to the invention, the reaction temperatures canbe varied within a certain range. In general, the process is carried outat temperatures between −150° C. and −50° C., preferably between −120°C. and −80° C.

The reaction according to the invention is preferably carried out underinert gas such as, in particular, nitrogen or argon.

When carrying out the process according to the invention, thephenyloxy(thio)ketones of the formula (VI) and the halides of theformula (VII) are employed in approximately equimolar amounts; however,it is possible to be above or below this ratio by up to about 20 molpercent. The organic alkali metal compound is advantageously employed inan excess of from 5 to 75 mol percent, preferably from 10 to 50 molpercent.

Here, the organic alkali metal compound may initially be allowed toreact with the halide of the formula (VII), and the keto compound of theformula (VI) may then be added; however, it is also possible toinitially charge the keto compound and the halide and then to add theorganic alkali metal compound at low temperature (for example at from−100° C. to −130° C.). The isolation of the compounds of the formula(I-b) is carried out by hydrolyzing, with water, the alkali metalalkoxide (for example lithium alkoxide) initially formed in thereaction. Further work-up is then carried out in a customary manner.

Process D

The bromides of the formula (VIII) are known. The (thio)phenols of theformula (V) are likewise known.

The phenyl(oxy/thio)ketones of the formula (IX) where Z does notrepresent bromine if X⁴ represents 3-pyridinyl occurring asintermediates for carrying out the process D according to the inventionare novel. They can be prepared in a known manner (cf. JP-A 62-084061,WO 01/87878).

The organometal compounds of the formula (X) are known, where M informula (X) preferably represents lithium or magnesium.

The process D (step 1) according to the invention is carried out in thepresence of a diluent and, if appropriate, in the presence of a base.Suitable diluents for the reaction according to the invention are allorganic solvents which are inert. These preferably include alcohols,such as, for example, ethanol and methoxyethanol; ketones, such as, forexample, 2-butanone; nitriles, such as, for example, acetonitrile;esters, such as, for example, ethyl acetate; ethers, such as, forexample, dioxane; aromatic hydrocarbons, such as, for example, benzeneand toluene; or amides, such as, for example, dimethylformamide.

Suitable bases for the reaction according to the invention are allorganic and inorganic bases which can customarily be used. Thesepreferably include alkali metal carbonates, such as, for example, sodiumcarbonate or potassium carbonate; alkali metal hydroxides, such as, forexample, sodium hydroxide; alkali metal alkoxides, such as, for example,sodium methoxide and potassium methoxide and sodium ethoxide andpotassium ethoxide; alkali metal hydrides, such as, for example, sodiumhydride; and also lower tertiary alkylamines, cycloalkylamines andaralkylamines, such as, in particular, triethylamine.

When carrying out the process according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures between 0° C. and 200° C.,preferably between 20° C. and 100° C.

If appropriate, the reaction according to the invention can be carriedout under elevated pressure. In general, the reaction is carried outbetween 1 and 50 bar, preferably between 1 and 25 bar.

When carrying out the process D (step 1) according to the invention,preferably from 1 to 2 mol of (thio)phenol of the formula (V) and, ifappropriate, from 1 to 3 mol of base are employed per mole ofbromoketone of the general formula (VIII). The isolation of the endproducts is carried out in a generally customary manner.

The process D (step 2) according to the invention is carried out in thepresence of a diluent and in the presence of an organic alkali metalcompound. If appropriate, an acid or a metal salt is then added to thecompound of the formula (I-k) obtained (see below).

Preferred diluents for the conversion according to the invention ofcompounds of the formula (IX) into compounds of the formula (I-k) areinert organic solvents. These include in particular ethers, such asdiethyl ether or tetrahydrofuran. Preferred organic alkali metalcompounds used for the reaction according to the invention are alkalineearth metal alkyls, such as, in particular, t-butylmagnesium chloride;however, it is also possible to use alkali metal alkyls, such ast-butyllithium.

In the process according to the invention, the reaction temperatures canbe varied within a certain range. In general, the process is carried outat temperatures between −100° C. and +20° C., preferably between −78° C.and 0° C.

The reaction according to the invention is preferably carried out underinert gas such as, in particular, nitrogen or argon.

When carrying out the process according to the invention, the ketones ofthe formula (IX) and the organometal compounds of the formula (X) areemployed in approximately equimolar amounts; however, it is possible tobe above or below this ratio by up to about 20 mol percent. Theorganometal compound is advantageously employed in an excess of from 5to 75 mol percent, preferably from 10 to 50 mol percent.

Here, the ketone (IX) may be initially charged, and the organometalcompound of the formula (X) may then be added at a suitable temperature(for example 0° C.). The isolation of the compounds of the formula (I-k)is carried out by hydrolyzing, with water, the metal alkoxide (forexample magnesium alkoxide) initially formed in the reaction. Furtherwork-up is then carried out in a customary manner.

Process E

The conversion of the phenyl(oxy/thio)alkanol derivatives of the formula(I-c) into phenyl(oxy/thio)alkanol derivatives of the formula (I-e) canbe carried out by two different routes (cf. EP-A 0 793 657).

Phenyl(oxy/thio)alkanol derivatives of the formula (I-c) are either

(α) reacted successively with strong bases and sulphur in the presenceof a diluent and then hydrolyzed with water, if appropriate in thepresence of an acid, or(β) reacted with sulphur in the presence of a high-boiling diluent andthen, if required, treated with water and, if required, with acid.

Suitable bases for carrying out the process E, variant (α), according tothe invention are all strong alkali metal bases customary for suchreactions. Preference is given to using n-butyllithium, lithiumdiisopropylamide, sodium hydride, sodium amide and also potassiumtert-butoxide in a mixture with tetrame-thylethylenediamine (=TMEDA).

Suitable diluents for carrying out the process E, variant (α), accordingto the invention are all inert organic solvents customary for suchreactions. Preference is given to using ethers, such as tetrahydrofuran,dioxane, diethyl ether and 1,2-dimethoxyethane, furthermore liquidammonia or else strongly polar solvents, such as dimethyl sulphoxide.

Sulphur is preferably employed in the form of a powder. When carryingout the process E, variant (α), according to the invention, water, ifappropriate in the presence of an acid, is used for carrying out thehydrolysis. Suitable acids are all inorganic or organic acids customaryfor such reactions. Preference is given to using acetic acid, dilutesulphuric acid and dilute hydrochloric acid. However, it is alsopossible to carry out the hydrolysis with aqueous ammonium chloridesolution.

When carrying out the variant (α), the reaction temperatures may bevaried within a certain range. In general, the variant is carried out attemperatures between −70° C. and +20° C., preferably between −70° C. and0° C.

The process E according to the invention is generally carried out underatmospheric pressure. However, it is also possible to operate underelevated or reduced pressure. Thus, when carrying out variant (α), it ispossible in particular to operate under elevated pressure.

When carrying out the process E according to the invention according tovariant (α), in general from 2 to 3 equivalents, preferably from 2.0 to2.5 equivalents, of strong base and subsequently an equivalent amount orelse an excess of sulphur are employed per mole ofphenyl(oxy/thio)alkanol derivatives of the formula (I-c). The reactionmay be carried out under an atmosphere of protective gas, for exampleunder nitrogen or argon. Work-up is carried out by customary methods.

Suitable diluents for carrying out the process E, variant (β), accordingto the invention are all high-boiling organic solvents customary forsuch reactions. Preference is given to using amides, such asdimethylformamide and dimethylacetamide, moreover heterocycliccompounds, such as N-methylpyrrolidone, and also ethers, such asdiphenyl ether.

When carrying out the process E according to the invention according tovariant (β), sulphur is also generally employed in the form of a powder.After the reaction, treatment with water and, if appropriate, acid mayoptionally be carried out. This takes place like the hydrolysis whencarrying out variant (α).

When carrying out the process E, variant (β), according to theinvention, the reaction temperatures can likewise be varied within arelatively wide range. In general, the variant is carried out attemperatures between 150° C. and 300° C., preferably between 180° C. and250° C.

When carrying out the process E according to the invention according tovariant (β), in general from 1 to 5 mol, preferably from 1.5 to 3 mol,of sulphur are employed per mole of phenyl(oxy/thio)alkanol derivativesof the formula (I-c). Work-up is carried out by customary methods.

The compounds of the general formula (I) which can be obtained by theprocesses A to E according to the invention can be converted into acidaddition salts or metal salt complexes.

Suitable for producing physiologically acceptable acid addition salts ofthe compounds of the general formula (I) are preferably the followingacids: hydrohalic acids, such as, for example, hydrochloric acid andhydrobromic acid, in particular hydrochloric acid, furthermorephosphoric acid, nitric acid, sulphuric acid, mono- and bifunctionalcarboxylic acids and hydroxycarboxylic acids, such as, for example,acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid,citric acid, salicylic acid, sorbic acid, lactic acid and also sulphonicacids, such as, for example, p-toluenesulphonic acid and1,5-naphthalenedisulphonic acid.

The acid addition salts of the compounds of the general formula (I) canbe obtained in a simple manner by customary methods for forming salts,for example by dissolving a compound of the general formula (I) in asuitable inert solvent and adding the acid, for example hydrochloricacid, and be isolated in a known manner, for example by filtration, and,if required, be purified by washing with an inert organic solvent.

Preferred for preparing metal salt complexes of the 65 compounds of thegeneral formula (I) are salts of metals of the II to IV main group andthe I and II and the IV to VIII transition group of the Periodic System,examples which may be mentioned being copper, zinc, manganese,magnesium, tin, iron and nickel.

Suitable anions of the salts are those which are preferably derived fromthe following acids: hydrohalic acids, such as, for example,hydrochloric acid and hydrobromic acid, furthermore phosphoric acid,nitric acid and sulphuric acid.

The metal salt complexes of compounds of the general formula (I) can beobtained in a simple manner by customary processes, for example bydissolving the metal salt in alcohol, for example ethanol, and addingthe solution to the compound of the general formula (I). Metal saltcomplexes can be isolated in a known manner, for example by filtration,and, if required, be purified by recrystallization.

The present invention furthermore relates to a composition forcontrolling unwanted microorganisms which comprises the active compoundsaccording to the invention. These are preferably fungicidal compositionswhich comprise agriculturally suitable auxiliaries, solvents, carriers,surfactants or extenders.

Moreover, the invention relates to a method for controlling unwantedmicroorganisms, characterized in that the active compounds according tothe invention are applied to the phytopathogenic fungi and/or theirhabitat.

According to the invention, a carrier is a natural or synthetic organicor inorganic substance with which the active compounds are mixed orbonded for better applicability, in particular for application to plantsor plant parts or seed. The carrier, which may be solid or liquid, isgenerally inert and should be suitable for use in agriculture.

Suitable solid or liquid carriers are: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and natural orsynthetic silicates, resins, waxes, solid fertilizers, water, alcohols,especially butanol, organic solvents, mineral and vegetable oils andderivatives of these. Mixtures of such carriers may also be used.Suitable solid carriers for granules are: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepiolite,dolomite, and synthetic granules of inorganic and organic meals, andalso granules of organic material such as sawdust, coconut shells, maizecobs and tobacco stalks.

Suitable liquefied gaseous extenders or carriers are liquids which aregaseous at ambient temperature and under atmospheric pressure, forexample aerosol propellants, such as halogenated hydrocarbons, and alsobutane, propane, nitrogen and carbon dioxide.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Essentially, suitableliquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes ordichloro-methane, aliphatic hydrocarbons such as cyclohexane orparaffins, for example mineral oil fractions, mineral and vegetableoils, alcohols such as butanol or glycol and their ethers and esters,ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents such as dimethylformamide anddimethyl sulfoxide, and also water.

The compositions according to the invention may comprise additionalfurther components, such as, for example, surfactants. Suitablesurfactants are emulsifiers and/or foam formers, dispersants or wettingagents having ionic or nonionic properties, or mixtures of thesesurfactants. Examples of these are salts of polyacrylic acid, salts oflignosulphonic acid, salts of phenolsulphonic acid ornaphthalenesulphonic acid, poly-condensates of ethylene oxide with fattyalcohols or with fatty acids or with fatty amines, substituted phenols(preferably alkylphenols or arylphenols), salts of sulphosuccinicesters, taurine derivatives (preferably alkyl taurates), phosphoricesters of polyethoxylated alcohols or phenols, fatty esters of polyols,and derivatives of the compounds containing sulphates, sulphonates andphosphates, for example alkylaryl polyglycol ethers, alkylsulphonates,alkyl sulphates, arylsulphonates, protein hydrolysates, lignosulphitewaste liquors and methylcellulose. The presence of a surfactant isrequired if one of the active compounds and/or one of the inert carriersis insoluble in water and when the application takes place in water. Theproportion of surfactants is between 5 and 40 percent by weight of thecomposition according to the invention.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic colorants suchas alizarin colorants, azo colorants and metal phthalocyanine colorants,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

If appropriate, other additional components may also be present, forexample protective colloids, binders, adhesives, thickeners, thixotropicsubstances, penetrants, stabilizers, sequestering agents, complexformers. In general, the active compounds can be combined with any solidor liquid additive customarily used for formulation purposes.

The compositions and formulations according to the invention generallycomprise between 0.05 and 99% by weight, 0.01 and 98% by weight,preferably between 0.1 and 95% by weight, particularly preferablybetween 0.5 and 90% of active compound, very particularly preferablybetween 10 and 70% by weight.

The active compounds or compositions according to the invention can beused as such or, depending on their respective physical and/or chemicalproperties, in the form of their formulations or the use forms preparedtherefrom, such as aerosols, capsule suspensions, cold-foggingconcentrates, warm-fogging concentrates, encapsulated granules, finegranules, flowable concentrates for the treatment of seed, ready-to-usesolutions, dustable powders, emulsifiable concentrates, oil-in-wateremulsions, water-in-oil emulsions, macrogranules, microgranules,oil-dispersible powders, oil-miscible flowable concentrates,oil-miscible liquids, foams, pastes, pesticide coated seed, suspensionconcentrates, suspoemulsion concentrates, soluble concentrates,suspensions, wettable powders, soluble powders, dusts and granules,water-soluble granules or tablets, water-soluble powders for thetreatment of seed, wettable powders, natural products and syntheticsubstances impregnated with active compound, and alsomicroencapsulations in polymeric substances and in coating materials forseed, and also ULV cold-fogging and warm-fogging formulations.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one customaryextender, solvent or diluent, emulsifier, dispersant, and/or binder orfixative, wetting agent, water repellent, if appropriate desiccants andUV stabilizers and, if appropriate, dyes and pigments, defoamers,preservatives, secondary thickeners, adhesives, gibberellins and alsofurther processing auxiliaries.

The compositions according to the invention include not onlyformulations which are already ready for use and can be applied with asuitable apparatus to the plant or the seed, but also commercialconcentrates which have to be diluted with water prior to use.

The active compounds according to the invention can be present as suchor in their (commercial) formulations and in the use forms prepared fromthese formulations as a mixture with other (known) active compounds,such as insecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

The treatment according to the invention of the plants and plant partswith the active compounds or compositions is carried out directly or byaction on their surroundings, habitat or storage space using customarytreatment methods, for example by dipping, spraying, atomizing,irrigating, evaporating, dusting, fogging, broadcasting, foaming,painting, spreading-on, watering (drenching), drip irrigating and, inthe case of propagation material, in particular in the case of seeds,furthermore as a powder for dry seed treatment, a solution for seedtreatment, a water-soluble powder for slurry treatment, by incrusting,by coating with one or more coats, etc. It is furthermore possible toapply the active compounds by the ultra-low volume method or to injectthe active compound preparation or the active compound itself into thesoil.

The invention furthermore includes a method for treating seed.

The invention furthermore relates to seed which has been treated inaccordance with one of the methods described in the previous paragraph.The seeds according to the invention are used in methods for theprotection of seed from undesirable microorganisms. In these methods,seed treated with at least one active compound according to theinvention is employed.

The active compounds or compositions according to the invention are alsosuitable for treating seed. A large part of the damage to crop plantscaused by harmful organisms is triggered by the infection of the seedduring storage or after sowing both during and after germination of theplant. This phase is particularly critical since the roots and shoots ofthe growing plant are particularly sensitive, and even small damage mayresult in the death of the plant. Accordingly, there is great interestin protecting the seed and the germinating plant by using appropriatecompositions.

The control of phytopathogenic fungi by treating the seed of plants hasbeen known for a long time and is the subject of continuousimprovements. However, the treatment of seed entails a series ofproblems which cannot always be solved in a satisfactory manner. Thus,it is desirable to develop methods for protecting the seed and thegerminating plant which dispense with, or at least reduce considerably,the additional application of crop protection agents after planting orafter emergence of the plants. It is furthermore desirable to optimizethe amount of active compound employed in such a way as to provideoptimum protection for the seed and the germinating plant from attack byphytopathogenic fungi, but without damaging the plant itself by theactive compound employed. In particular, methods for the treatment ofseed should also take into consideration the intrinsic fungicidalproperties of transgenic plants in order to achieve optimum protectionof the seed and the germinating plant with a minimum of crop protectionagents being employed.

The present invention therefore also relates to a method for theprotection of seed and germinating plants, from attack byphytopathogenic fungi, by treating the seed with a composition accordingto the invention. The invention also relates to the use of thecompositions according to the invention for treating seed for protectingthe seed and the germinating plant against phytopathogenic fungi.Furthermore, the invention relates to seed treated with a compositionaccording to the invention for protection against phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergenceis carried out primarily by treating the soil and the above-ground partsof plants with crop protection agents. Owing to the concerns regarding apossible impact of the crop protection agents on the environment and thehealth of humans and animals, there are efforts to reduce the amount ofactive compounds applied.

One of the advantages of the present invention is that the particularsystemic properties of the active compounds and compositions accordingto the invention mean that treatment of the seed with these activecompounds and compositions not only protects the seed itself, but alsothe resulting plants after emergence, from phytopathogenic fungi. Inthis manner, the immediate treatment of the crop at the time of sowingor shortly thereafter can be dispensed with.

It is also considered to be advantageous that the active compounds orcompositions according to the invention can be used in particular alsofor transgenic seed where the plant growing from this seed is capable ofexpressing a protein which acts against pests. By treating such seedwith the active compounds or compositions according to the invention,even by the expression of the, for example, insecticidal protein,certain pests may be controlled. Surprisingly, a further synergisticeffect may be observed here, which additionally increases theeffectiveness of the protection against attack by pests.

The compositions according to the invention are suitable for protectingseed of any plant variety which is employed in agriculture, in thegreenhouse, in forests or in horticulture and viticulture. Inparticular, this takes the form of seed of cereals (such as wheat,barley, rye, triticale, sorghum/millet and oats), maize, cotton, soyabeans, rice, potatoes, sunflower, bean, coffee, beet (for example sugarbeet and fodder beet), peanut, oilseed rape, poppy, olive, coconut,cacao, sugar cane, tobacco, vegetables (such as tomato, cucumbers,onions and lettuce), turf and ornamentals (see also hereinbelow). Thetreatment of the seed of cereals (such as wheat, barley, rye, triticaleand oats), maize and rice is of particular importance.

As also described further below, the treatment of transgenic seed withthe active compounds or compositions according to the invention is ofparticular importance. This refers to the seed of plants containing atleast one heterologous gene which allows the expression of a polypeptideor protein having insecticidal properties. The heterologous gene intransgenic seed can originate, for example, from microorganisms of thespecies Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma,Clavibacter, Glomus or Gliocladium. Preferably, this heterologous geneis from Bacillus sp., the gene product having activity against theEuropean corn borer and/or the Western corn rootworm. Particularlypreferably, the heterologous gene originates from Bacillusthuringiensis.

Within the context of the present invention, the composition accordingto the invention is applied to the seed either alone or in a suitableformulation. Preferably, the seed is treated in a state in which it isstable enough to avoid damage during treatment. In general, the seed maybe treated at any point in time between harvest and sowing. The seedusually used has been separated from the plant and freed from cobs,shells, stalks, coats, hairs or the flesh of the fruits. Thus, it ispossible to use, for example, seed which has been harvested, cleaned anddried to a moisture content of less than 15% by weight. Alternatively,it is also possible to use seed which, after drying, has been treated,for example, with water and then dried again.

When treating the seed, care must generally be taken that the amount ofthe composition according to the invention applied to the seed and/orthe amount of further additives is chosen in such a way that thegermination of the seed is not adversely affected, or that the resultingplant is not damaged. This must be borne in mind in particular in thecase of active compounds which can have phytotoxic effects at certainapplication rates.

The compositions according to the invention can be applied directly,i.e. without any other components and undiluted. In general, it ispreferred to apply the compositions to the seed in the form of asuitable formulation. Suitable formulations and methods for treatingseed are known to the person skilled in the art and are described, forexample, in the following documents: U.S. Pat. No. 4,272,417 A, U.S.Pat. No. 4,245,432 A, U.S. Pat. No. 4,808,430 A, U.S. Pat. No. 5,876,739A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.

The active compounds which can be used in accordance with the inventioncan be converted into the customary seed-dressing formulations, such assolutions, emulsions, suspensions, powders, foams, slurries or othercoating materials for seed, and also ULV formulations

These formulations are prepared in a known manner, by mixing the activecompounds with customary additives such as, for example, customaryextenders and also solvents or diluents, colorants, wetting agents,dispersants, emulsifiers, antifoams, preservatives, secondarythickeners, adhesives, gibberellins and also water.

Colorants which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all colorants which arecustomary for such purposes. In this context, not only pigments, whichare sparingly soluble in water, but also dyes, which are soluble inwater, may be used. Examples which may be mentioned are the colorantsknown by the names Rhodamin B, C.I. Pigment Red 112 and C.I. Solvent Red1.

Suitable wetting agents which may be present in the seed-dressingformulations which can be used in accordance with the invention are allsubstances which promote wetting and which are conventionally used forthe formulation of agrochemical active compounds. Preference is given tousing alkylnaphthalenesulphonates, such as diisopropyl- ordiisobutylnaphthalenesulphonates.

Suitable dispersants and/or emulsifiers which may be present in theseed-dressing formulations which can be used in accordance with theinvention are all nonionic, anionic and cationic dispersantsconventionally used for the formulation of agrochemical activecompounds. Preference is given to using nonionic or anionic dispersantsor mixtures of nonionic or anionic dispersants. Suitable nonionicdispersants which may be mentioned are, in particular, ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ether, and their phosphated or sulphatedderivatives. Suitable anionic dispersants are, in particular,lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Antifoams which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all foam-inhibitingsubstances conventionally used for the formulation of agrochemicalactive compounds. Silicone antifoams and magnesium stearate canpreferably be used.

Preservatives which may be present in the seed-dressing formulationswhich can be used in accordance with the invention are all substanceswhich can be employed for such purposes in agrochemical compositions.Dichlorophene and benzyl alcohol hemiformal may be mentioned by way ofexample.

Secondary thickeners which may be present in the seed-dressingformulations which can be used in accordance with the invention are allsubstances which can be employed for such purposes in agrochemicalcompositions. Cellulose derivatives, acrylic acid derivatives, xanthan,modified clays and finely divided silica are preferred.

Adhesives which may be present in the seed-dressing formulations whichcan be used in accordance with the invention are all customary binderswhich can be employed in seed-dressing products. Polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned asbeing preferred.

Gibberellins which can be present in the seed-dressing formulationswhich can be used in accordance with the invention are preferably thegibberellins A1, A3 (=gibberellic acid), A4 and A7; gibberellic acid isespecially preferably used. The gibberellins are known (cf. R. Wegler“Chemie der Pflanzenschutz- and Schädlingsbekämpfungsmittel” [Chemistryof crop protection agents and pesticides], vol. 2, Springer Ver-lag,1970, p. 401-412).

The seed-dressing formulations which can be used in accordance with theinvention can be employed for the treatment of a wide range of seed,including the seed of transgenic plants, either directly or afterpreviously having been diluted with water. In this context, additionalsynergistic effects may also occur in cooperation with the substancesformed by expression.

All mixers which can conventionally be employed for the seed-dressingoperation are suitable for treating seed with the seed-dressingformulations which can be used in accordance with the invention or withthe preparations prepared therefrom by addition of water. Specifically,a procedure is followed during the seed-dressing operation in which theseed is placed into a mixer, the specific desired amount ofseed-dressing formulations, either as such or after previously havingbeen diluted with water, is added, and everything is mixed until theformulation is distributed uniformly on the seed. If appropriate, thisis followed by a drying process.

The active compounds or compositions according to the invention have apotent microbicidal activity and can be employed for controllingundesirable microorganisms, such as fungi and bacteria, in cropprotection and in the protection of materials.

Fungicides can be employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

The fungicidal compositions according to the invention can be used forthe curative or protective control of phytopathogenic fungi.Accordingly, the invention also relates to curative and protectivemethods for controlling phytopathogenic fungi using the active compoundsor compositions according to the invention, which are applied to theseed, the plant or plant parts, the fruit or the soil in which theplants grow.

The compositions according to the invention for controllingphytopathogenic fungi in crop protection comprise an effective, butnon-phytotoxic amount of the active compounds according to theinvention. “Effective, but non-phytotoxic amount” means an amount of thecomposition according to the invention which is sufficient to controlthe fungal disease of the plant in a satisfactory manner or to eradicatethe fungal disease completely, and which, at the same time, does notcause any significant symptoms of phytotoxicity. In general, thisapplication rate may vary within a relatively wide range. It depends ona plurality of factors, for example on the fungus to be controlled, theplant, the climatic conditions and the ingredients of the compositionsaccording to the invention.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

All plants and plant parts can be treated in accordance with theinvention. By plants are understood here all plants and plantpopulations such as desired and undesired wild plants or crop plants(including naturally occurring crop plants). Crop plants can be plantswhich can be obtained by conventional breeding and optimization methodsor by biotechnological and genetic engineering methods or combinationsof these methods, including the transgenic plants and including theplant varieties which can or cannot be protected by varietal propertyrights. Plant parts are to be understood as meaning all parts and organsof plants above and below the ground, such as shoot, leaf, flower androot, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.Parts of plants also include harvested plants and vegetative andgenerative propagation material, for example seedlings, tubers,rhizomes, cuttings and seeds.

The active compounds according to the invention are suitable for theprotection of plants and plant organs, for increasing the harvestyields, for improving the quality of the harvested crop, while beingwell tolerated by plants, having favourable toxicity to warm-bloodedspecies and being environmentally friendly. They may be preferablyemployed as crop protection agents. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment.

The following plants may be mentioned as plants which can be treatedaccording to the invention: cotton, flax, grapevine, fruit, vegetables,such as Rosaceae sp. (for example pome fruits such as apples and pears,but also stone fruits such as apricots, cherries, almonds and peaches,and soft fruits such as strawberries), Ribesioidae sp., Juglandaceaesp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp.,Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for examplebanana plants and banana plantations), Rubiaceae sp. (for examplecoffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for examplelemons, oranges and grapefruit); Solanaceae sp. (for example tomatoes),Liliaceae sp., Asteraceae sp. (for example lettuce), Umbelliferae sp.,Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (for examplecucumbers), Alliaceae sp. (for example leeks, onions), Papilionaceae sp.(for example peas); major crop plants such as Gramineae sp. (for examplemaize, turf, cereals such as wheat, rye, rice, barley, oats, millet andtriticale), Asteraceae sp. (for example sunflower), Brassicaceae sp.(for example white cabbage, red cabbage, broccoli, cauliflower, Brusselssprouts, pak choi, kohlrabi, small radishes, and also oilseed rape,mustard, horseradish and cress), Fabacae sp. (for example beans,peanuts), Papilionaceae sp. (for example soya beans), Solanaceae sp.(for example potatoes), Chenopodiaceae sp. (for example sugar beet,fodder beet, Swiss chard, beetroot); useful plants and ornamental plantsin gardens and forests; and in each case genetically modified types ofthese plants.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are to be understood as meaning plants havingnew properties (“traits”) and which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. They can becultivars, varieties, bio- or genotypes.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants inwhich a heterologous gene has been stably integrated into the genome.The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for exampleantisense technology, cosuppression technology or RNAi technology [RNAinterference]). A heterologous gene that is located in the genome isalso called a transgene. A transgene that is defined by its particularlocation in the plant genome is called a transformation or transgenicevent.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Possible are thus, for example, the followingeffects which exceed the effects which were to be expected: reducedapplication rates and/or a widening of the activity spectrum and/or anincrease in the activity of the active compounds and compositions whichcan be used according to the invention, better plant growth, increasedtolerance to high or low temperatures, increased tolerance to drought orto water or soil salt content, increased flowering performance, easierharvesting, accelerated maturation, higher harvest yields, biggerfruits, larger plant height, greener leaf colour, earlier flowering,higher quality and/or a higher nutritional value of the harvestedproducts, higher sugar concentration within the fruits, better storagestability and/or processability of the harvested products.

At certain application rates, the active compounds according to theinvention may also have a strengthening effect in plants. Accordingly,they are suitable for mobilizing the defence system of the plant againstattack by unwanted phytopathogenic fungi and/or microorganisms and/orviruses. This may, if appropriate, be one of the reasons for theenhanced activity of the combinations according to the invention, forexample against fungi. Plant-strengthening (resistance-inducing)substances are to be understood as meaning, in the present context, alsothose substances or combinations of substances which are capable ofstimulating the defence system of plants in such a way that, whensubsequently inoculated with unwanted phytopathogenic fungi, the treatedplants display a substantial degree of resistance to these unwantedphytopathogenic fungi. Thus, the substances according to the inventioncan be employed for protecting plants against attack by theabovementioned pathogens within a certain period of time after thetreatment. The period within which protection is brought about generallyextends from 1 to 10 days, preferably 1 to 7 days, after the treatmentof the plants with the active compounds.

Plants and plant varieties which are preferably treated according to theinvention include all plants which have genetic material which impartsparticularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant varieties which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstress factors, i.e. said plants have a better defence against animaland microbial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant varieties which may also be treated according to theinvention are those plants which are resistant to one or more abioticstress factors. Abiotic stress conditions may include, for example,drought, cold temperature exposure, heat exposure, osmotic stress,waterlogging, increased soil salinity, increased exposure to minerals,exposure to ozone, exposure to strong light, limited availability ofnitrogen nutrients, limited availability of phosphorus nutrients orshade avoidance.

Plants and plant varieties which may also be treated according to theinvention are those plants characterized by enhanced yieldcharacteristics. Enhanced yield in said plants can be the result of, forexample, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigour, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristics of heterosis, or hybrid vigour,which results in generally higher yield, vigour, health and resistancetowards biotic and abiotic stress factors. Such plants are typicallymade by crossing an inbred male-sterile parent line (the female parent)with another inbred male-fertile parent line (the male parent). Hybridseed is typically harvested from the male sterile plants and sold togrowers. Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling (i.e. the mechanical removal of the male reproductive organsor male flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plants,it is typically useful to ensure that male fertility in hybrid plants,which contain the genetic determinants responsible for male sterility,is fully restored. This can be accomplished by ensuring that the maleparents have appropriate fertility restorer genes which are capable ofrestoring the male fertility in hybrid plants that contain the geneticdeterminants responsible for male sterility. Genetic determinants formale sterility may be located in the cytoplasm. Examples of cytoplasmicmale sterility (CMS) were for instance described for Brassica species.However, genetic determinants for male sterility can also be located inthe nuclear genome. Male sterile plants can also be obtained by plantbiotechnology methods such as genetic engineering. A particularly usefulmeans of obtaining male sterile plants is described in WO 89/10396 inwhich, for example, a ribonuclease such as a barnase is selectivelyexpressed in the tapetum cells in the stamens. Fertility can then berestored by expression in the tapetum cells of a ribonuclease inhibitorsuch as barstar.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containing naturallyoccurring mutations of the abovementioned genes.

Other herbicide-resistant plants are for example plants which have beenmade tolerant to herbicides inhibiting the enzyme glutamine synthase,such as bialaphos, phosphinothricin or glufosinate. Such plants can beobtained by expressing an enzyme detoxifying the herbicide or a mutantglutamine synthase enzyme that is resistant to inhibition. One suchefficient detoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase have been described.

Further herbicide-tolerant plants are also plants that have been madetolerant to the herbicides inhibiting the enzymehydroxyphenylpyruvatedioxygenase (HPPD).Hydroxyphenylpyruvatedioxygenases are enzymes that catalyse the reactionin which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD inhibitors can be transformedwith a gene encoding a naturally occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme. Tolerance to HPPD inhibitors canalso be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD inhibitor. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme.

Further herbicide-resistant plants are plants that have been madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitorsinclude, for example, sulphonylurea, imidazolinone, triazolopyrimidines,pyrimidinyl oxy(thio)benzoates, and/orsulphonylaminocarbonyltriazolinone herbicides. Different mutations inthe ALS enzyme (also known as acetohydroxyacid synthase, AHAS) are knownto confer tolerance to different herbicides and groups of herbicides.The production of sulphonylurea-tolerant plants andimidazolinone-tolerant plants has been described in the internationalpublication WO 1996/033270. Further sulphonylurea- andimidazolinone-tolerant plants have also been described, for example inWO 2007/024782.

Other plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, by selection in cell cultures in thepresence of the herbicide or by mutation breeding.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

In the present context, the term “insect-resistant transgenic plant”includes any plant containing at least one transgene comprising a codingsequence encoding:

-   1) an insecticidal crystal protein from Bacillus thuringiensis or an    insecticidal portion thereof, such as the insecticidal crystal    proteins listed online at:    http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or    insecticidal portions thereof, for example proteins of the Cry    protein classes Cry 1Ab, Cry 1Ac, Cry1F, Cry2Ab, Cry3Ae or Cry3Bb or    insecticidal portions thereof; or-   2) a crystal protein from Bacillus thuringiensis or a portion    thereof which is insecticidal in the presence of a second other    crystal protein from Bacillus thuringiensis or a portion thereof,    such as the binary toxin made up of the Cy34 and Cy35 crystal    proteins; or-   3) a hybrid insecticidal protein comprising parts of two different    insecticidal crystal proteins from Bacillus thuringiensis, such as a    hybrid of the proteins of 1) above or a hybrid of the proteins of 2)    above, for example the Cry1A.105 protein produced by maize event    MON98034 (WO 2007/027777); or-   4) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation, such as the Cry3Bb1 protein in maize events MON863    or MON88017, or the Cry3A protein in maize event MIR604;-   5) an insecticidal secreted protein from Bacillus thuringiensis or    Bacillus cereus, or an insecticidal portion thereof, such as the    vegetative insecticidal proteins (VIP) listed at:    http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html,    e.g. proteins from the VIP3Aa protein class; or-   6) a secreted protein from Bacillus thuringiensis or Bacillus cereus    which is insecticidal in the presence of a second secreted protein    from Bacillus thuringiensis or B. cereus, such as the binary toxin    made up of the VIP1A and VIP2A proteins;-   7) a hybrid insecticidal protein comprising parts from different    secreted proteins from Bacillus thuringiensis or Bacillus cereus,    such as a hybrid of the proteins in 1) above or a hybrid of the    proteins in 2) above; or-   8) a protein of any one of 1) to 3) above wherein some, particularly    1 to 10, amino acids have been replaced by another amino acid to    obtain a higher insecticidal activity to a target insect species,    and/or to expand the range of target insect species affected, and/or    because of changes induced in the encoding DNA during cloning or    transformation (while still encoding an insecticidal protein), such    as the VIP3Aa protein in cotton event COT102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay insect resistance developmentto the plants, by using different proteins insecticidal to the sametarget insect species but having a different mode of action, such asbinding to different receptor binding sites in the insect.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stress factors. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such stress resistance. Particularly usefulstress-tolerant plants include the following:

-   a. plants which contain a transgene capable of reducing the    expression and/or the activity of the poly(ADP-ribose)polymerase    (PARP) gene in the plant cells or plants;-   b. plants which contain a stress tolerance-enhancing transgene    capable of reducing the expression and/or the activity of the    PARG-encoding genes of the plants or plant cells;-   c. plants which contain a stress tolerance-enhancing transgene    coding for a plant-functional enzyme of the nicotinamide adenine    dinucleotide salvage biosynthesis pathway, including nicotinamidase,    nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide    adenyltransferase, nicotinamide adenine dinucleotide synthetase or    nicotinamide phosphoribosyltransferase.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as, for example:

-   1) Transgenic plants which synthesize a modified starch which is    altered with respect to its chemo-physical traits, in particular the    amylose content or the amylose/amylopectin ratio, the degree of    branching, the average chain length, the distribution of the side    chains, the viscosity behaviour, the gel resistance, the grain size    and/or grain morphology of the starch in comparison to the    synthesized starch in wild-type plant cells or plants, such that    this modified starch is better suited for certain applications.-   2) Transgenic plants which synthesize non-starch carbohydrate    polymers or which synthesize non-starch carbohydrate polymers with    altered properties in comparison to wild-type plants without genetic    modification. Examples are plants which produce polyfructose,    especially of the inulin and levan type, plants which produce    alpha-1,4-glucans, plants which produce alpha-1,6-branched    alpha-1,4-glucans, and plants producing alternan.-   3) Transgenic plants which produce hyaluronan.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as cotton plants, with altered fibrecharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfibre characteristics and include:

-   a) plants, such as cotton plants, which contain an altered form of    cellulose synthase genes,-   b) plants, such as cotton plants, which contain an altered form of    rsw2 or rsw3 homologous nucleic acids;-   c) plants, such as cotton plants, with an increased expression of    sucrose phosphate synthase;-   d) plants, such as cotton plants, with an increased expression of    sucrose synthase;-   e) plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fibre cell is altered, for    example through downregulation of fibre-selective β-1,3-glucanase;-   f) plants, such as cotton plants, which have fibres with altered    reactivity, for example through the expression of the    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as oilseed rape or related Brassica plants,with altered oil profile characteristics. Such plants can be obtained bygenetic transformation or by selection of plants containing a mutationimparting such altered oil characteristics and include:

a) plants, such as oilseed rape plants, which produce oil having a higholeic acid content;b) plants, such as oilseed rape plants, which produce oil having a lowlinolenic acid content;c) plants, such as oilseed rape plants, which produce oil having a lowlevel of saturated fatty acids.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins are the transgenic plants available under thefollowing trade names: YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), BiteGard® (for example maize),BT-Xtra® (for example maize), StarLink® (for example maize), Bollgard®(cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (forexample maize), Protecta® and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize varieties,cotton varieties and soya bean varieties which are available under thefollowing trade names: Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya beans), Liberty Link® (tolerance tophosphinothricin, for example oilseed rape), IMI® (tolerance toimidazolinone) and SCS® (tolerance to sulphonylurea, for example maize).Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield® (for example maize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, that are listed for example in thedatabases for various national or regional regulatory agencies (see forexample http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

Moreover, in the protection of materials, the active compounds orcompositions according to the invention can be employed for protectingindustrial materials against attack and destruction by unwantedmicroorganisms, such as, for example, fungi and insects.

Furthermore, the compounds according to the invention can be used aloneor in combinations with other active compounds as antifoulingcompositions.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper, wallpaper, and board,textiles, carpets, leather, wood, paints and plastic articles, coolinglubricants and other materials which can be infected with, or destroyedby, microorganisms. Parts of production plants and buildings, forexample cooling-water circuits, cooling and heating systems andventilation and air-conditioning units, which may be impaired by theproliferation of microorganisms may also be mentioned within the scopeof the materials to be protected. Industrial materials which may bementioned within the scope of the present invention are preferablyadhesives, sizes, paper and board, leather, wood, paints, coolinglubricants and heat-transfer liquids, particularly preferably wood. Theactive compounds or compositions according to the invention may preventdisadvantageous effects, such as rotting, decay, discoloration,decoloration or formation of mould. Moreover, the compounds according tothe invention can be employed for protecting objects which come intocontact with saltwater or brackish water, in particular hulls, screens,nets, buildings, moorings and signaling systems, against fouling.

The method according to the invention for controlling unwanted fungi canalso be employed for protecting storage goods. Here, storage goods areto be understood as meaning natural substances of vegetable or animalorigin or processed products thereof of natural origin, for whichlong-term protection is desired. Storage goods of vegetable origin, suchas, for example, plants or plant parts, such as stems, leaves, tubers,seeds, fruits, grains, can be protected freshly harvested or afterprocessing by (pre)drying, moistening, comminuting, grinding, pressingor roasting. Storage goods also include timber, both unprocessed, suchas construction timber, electricity poles and barriers, or in the formof finished products, such as furniture. Storage goods of animal originare, for example, hides, leather, furs and hairs. The active compoundsaccording to the invention may prevent disadvantageous effects, such asrotting, decay, discoloration, decoloration or formation of mould.

Some pathogens of fungal diseases which can be treated according to theinvention may be mentioned by way of example, but not by way oflimitation:

Diseases caused by powdery mildew pathogens, such as, for example,Blumeria species, such as, for example, Blumeria graminis; Podosphaeraspecies, such as, for example, Podosphaera leucotricha; Sphaerothecaspecies, such as, for example, Sphaerotheca fuliginea; Uncinula species,such as, for example, Uncinula necator;diseases caused by rust disease pathogens, such as, for example,Gymnosporangium species, such as, for example, Gymnosporangium sabinae;Hemileia species, such as, for example, Hemileia vastatrix; Phakopsoraspecies, such as, for example, Phakopsora pachyrhizi and Phakopsorameibomiae; Puccinia species, such as, for example, Puccinia recondita orPuccinia triticina; Uromyces species, such as, for example, Uromycesappendiculatus;diseases caused by pathogens from the group of the Oomycetes, such as,for example, Bremia species, such as, for example, Bremia lactucae;Peronospora species, such as, for example, Peronospora pisi or P.brassicae; Phytophthora species, such as, for example, Phytophthorainfestans; Plasmopara species, such as, for example, Plasmoparaviticola; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species,such as, for example, Pythium ultimum; leaf blotch diseases and leafwilt diseases caused, for example, by Alternaria species, such as, forexample, Alternaria solani; Cercospora species, such as, for example,Cercospora beticola; Cladiosporium species, such as, for example,Cladiosporium cucumerinum; Cochliobolus species, such as, for example,Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);Colletotrichum species, such as, for example, Colletotrichumlindemuthanium; Cycloconium species, such as, for example, Cycloconiumoleaginum; Diaporthe species, such as, for example, Diaporthe citri;Elsinoe species, such as, for example, Elsinoe fawcettii; Gloeosporiumspecies, such as, for example, Gloeosporium laeticolor; Glomerellaspecies, such as, for example, Glomerella cingulata; Guignardia species,such as, for example, Guignardia bidwelli; Leptosphaeria species, suchas, for example, Leptosphaeria maculans; Magnaporthe species, such as,for example, Magnaporthe grisea; Microdochium species, such as, forexample, Microdochium nivale; Mycosphaerella species, such as, forexample, Mycosphaerella graminicola and M. fijiensis; Phaeosphaeriaspecies, such as, for example, Phaeosphaeria nodorum; Pyrenophoraspecies, such as, for example, Pyrenophora teres; Ramularia species,such as, for example, Ramularia collo-cygni; Rhynchosporium species,such as, for example, Rhynchosporium secalis; Septoria species, such as,for example, Septoria apii; Typhula species, such as, for example,Typhula incarnata; Venturia species, such as, for example, Venturiainaequalis;root and stem diseases caused, for example, by Corticium species, suchas, for example, Corticium graminearum; Fusarium species, such as, forexample, Fusarium oxysporum; Gaeumannomyces species, such as, forexample, Gaeumannomyces graminis; Rhizoctonia species, such as, forexample, Rhizoctonia solani; Tapesia species, such as, for example,Tapesia acuformis; Thielaviopsis species, such as, for example,Thielaviopsis basicola;ear and panicle diseases (including corn cobs) caused, for example, byAlternaria species, such as, for example, Alternaria spp.; Aspergillusspecies, such as, for example, Aspergillus flavus; Cladosporium species,such as, for example, Cladosporium cladosporioides; Claviceps species,such as, for example, Claviceps purpurea; Fusarium species, such as, forexample, Fusarium culmorum; Gibberella species, such as, for example,Gibberella zeae; Monographella species, such as, for example,Monographella nivalis; Septoria species, such as, for example, Septorianodorum;diseases caused by smut fungi, such as, for example, Sphacelothecaspecies, such as, for example, Sphacelotheca reiliana; Tilletia species,such as, for example, Tilletia caries, T. controversa; Urocystisspecies, such as, for example, Urocystis occulta; Ustilago species, suchas, for example, Ustilago nuda, U. nuda tritici;fruit rot caused, for example, by Aspergillus species, such as, forexample, Aspergillus flavus; Botrytis species, such as, for example,Botrytis cinerea; Penicillium species, such as, for example, Penicilliumexpansum and P. purpurogenum; Sclerotinia species, such as, for example,Sclerotinia sclerotiorum; Verticilium species, such as, for example,Verticilium alboatrum;seed- and soil-borne rot and wilt diseases, and also diseases ofseedlings, caused, for example, by Fusarium species, such as, forexample, Fusarium culmorum; Phytophthora species, such as, for example,Phytophthora cactorum; Pythium species, such as, for example, Pythiumultimum; Rhizoctonia species, such as, for example, Rhizoctonia solani;Sclerotium species, such as, for example, Sclerotium rolfsii; cancerousdiseases, galls and witches' broom caused, for example, by Nectriaspecies, such as, for example, Nectria galligena;wilt diseases caused, for example, by Monilinia species, such as, forexample, Monilinia laxa; deformations of leaves, flowers and fruitscaused, for example, by Taphrina species, such as, for example, Taphrinadeformans;degenerative diseases of woody plants caused, for example, by Escaspecies, such as, for example, Phaeomoniella chlamydospora andPhaeoacremonium aleophilum and Fomitiporia mediterranea;diseases of flowers and seeds caused, for example, by Botrytis species,such as, for example, Botrytis cinerea;diseases of plant tubers caused, for example, by Rhizoctonia species,such as, for example, Rhizoctonia solani; Helminthosporium species, suchas, for example, Helminthosporium solani;diseases caused by bacterial pathogens, such as, for example,Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae; Pseudomonas species, such as, for example, Pseudomonas syringaepv. lachrymans; Erwinia species, such as, for example, Erwiniaamylovora.

Preference is given to controlling the following diseases of soya beans:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (Dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).

Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmospora vasinfecta), pod and stem blight (Diaporthephaseolorum), stem canker (Diaporthe phaseolorum var. caulivora),phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophoragregata), pythium rot (Pythium aphanidermatum, Pythium irregulare,Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctoniaroot rot, stem decay, and damping-off (Rhizoctonia solani), sclerotiniastem decay (Sclerotinia sclerotiorum), sclerotinia southern blight(Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discoloring andwood-destroying fungi (Basidiomycetes), and against slime organisms andalgae. Microorganisms of the following genera may be mentioned asexamples: Alternaria, such as Alternaria tenuis; Aspergillus, such asAspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora,such as Coniophora puetana; Lentinus, such as Lentinus tigrinus;Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporusversicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma,such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride;Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonasaeruginosa; Staphylococcus, such as Staphylococcus aureus.

In addition, the active compounds according to the invention also havevery good antimycotic activity. They have a very broad antimycoticactivity spectrum, in particular against dermatophytes and yeasts,moulds and diphasic fungi, (for example against Candida species, such asCandida albicans, Candida glabrata), and Epidermophyton floccosum,Aspergillus species, such as Aspergillus niger and Aspergillusfumigatus, Trichophyton species, such as Trichophyton mentagrophytes,Microsporon species such as Microsporon canis and audouinii. The list ofthese fungi by no means limits the mycotic spectrum covered, but is onlyfor illustration.

Accordingly, the active compounds according to the invention can be usedboth in medical and in non-medical applications.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the kind of application. The application rate of theactive compounds according to the invention is

-   -   when treating plant parts, for example leaves: from 0.1 to 10        000 g/ha, preferably from 10 to 1000 g/ha, particularly        preferably from 50 to 300 g/ha (when the application is carried        out by watering or dripping, it is even possible to reduce the        application rate, especially when inert substrates such as rock        wool or perlite are used);    -   when treating seed: from 2 to 200 g per 100 kg of seed,        preferably from 3 to 150 g per 100 kg of seed, particularly        preferably from 2.5 to 25 g per 100 kg of seed, very        particularly preferably from 2.5 to 12.5 g per 100 kg of seed;    -   when treating the soil: from 0.1 to 10 000 g/ha, preferably from        1 to 5000 g/ha.

These application rates are mentioned only by way of example and are notlimiting in the sense of the invention.

The active compounds or compositions according to the invention can thusbe employed for protecting plants for a certain period of time aftertreatment against attack by the pathogens mentioned. The period forwhich protection is provided extends generally for 1 to 28 days,preferably for 1 to 14 days, particularly preferably for 1 to 10 days,very particularly preferably for 1 to 7 days after the treatment of theplants with the active compounds, or for up to 200 days after a seedtreatment.

In addition, by the treatment according to the invention it is possibleto reduce the mycotoxin content in the harvested material and thefoodstuffs and feedstuffs prepared therefrom. Particular, but notexclusive, mention may be made here of the following mycotoxins:deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin,fumonisins, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol(DAS), beau-vericin, enniatin, fusaroproliferin, fusarenol, ochratoxins,patulin, ergot alkaloids and aflatoxins produced, for example, by thefollowing fungi: Fusarium spec., such as Fusarium acuminatum, F.avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberellazeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F.proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi,F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F.subglutinans, F. tricinctum, F. verticillioides, inter alia, and also byAspergillus spec., Penicillium spec., Claviceps purpurea, Stachybotrysspec., inter alia.

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides,safeners, growth regulators or agents to improve plant properties, or asmicrobicides, for example as fungicides, antimycotics, bactericides,viricides (including agents against viroids) or as agents against MLO(Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). Ifappropriate, they can also be used as intermediates or precursors forthe synthesis of other active compounds.

The active compounds according to the invention interfere with themetabolism of the plants and can therefore also be used as growthregulators.

Plant growth regulators may have various effects on plants. The effectof the compounds depends essentially on the time of application based onthe development stage of the plant and also on the amounts of activecompound applied to the plants or their environment and on the type ofapplication. In each case, growth regulators should have a certaindesired effect on the crop plants.

Plant growth-regulating compounds can be used, for example, forinhibiting the vegetative growth of the plants. Such an inhibition ofgrowth is of economic interest, for example, in the case of grasses, asit is thus possible to reduce the frequency of mowing the grass inornamental gardens, parks and sport facilities, on roadsides, atairports or in fruit cultures. Also of importance is the inhibition ofthe growth of herbaceous and woody plants on roadsides and in thevicinity of pipelines or overhead cables or quite generally in areaswhere strong plant growth is unwanted.

The use of growth regulators for inhibiting the longitudinal growth ofcereal is also of importance. In this way, it is possible to reduce oreliminate completely the risk of lodging of the plants prior to theharvest. Moreover, in cereals growth regulators may strengthen the culm,which also acts against lodging. The application of growth regulatorsfor stabilizing and strengthening culms permits the use of higherfertilizer application rates to increase the yield without any risk oflodging of cereals.

In many crop plants, inhibition of vegetative growth allows a morecompact planting, and it is thus possible to achieve higher yields basedon the soil surface. Another advantage of the smaller plants obtained inthis manner is that the crops are easier to cultivate and harvest.

Inhibition of the vegetative plant growth may also lead to increasedyields in that the nutrients and assimilates are of more benefit toflower and fruit formation than to the vegetative parts of the plants.

Frequently, growth regulators can also be used to promote vegetativegrowth. This is of great benefit when harvesting the vegetative plantparts. However, promoting the vegetative growth may also promote thegenerative growth in that more assimilates are formed, resulting in moreor larger fruits.

In some cases, yield increases may be achieved by manipulating themetabolism of the plant, without any changes of vegetative growth beingdetectable. Furthermore, growth regulators may be used to change thecomposition of the plants, which in turn may result in an improvedquality of the harvested products. Thus, it is possible, for example, toincrease the sugar content in sugar beet, sugar cane, pineapples andalso in citrus fruit, or to increase the protein content in soya beansor in cereals. It is also possible, for example, to inhibit, with growthregulators, the degradation of wanted ingredients, such as, for example,sugar in sugar beet or sugar cane, before or after harvest. Moreover,there can be a positive effect on the production or the elimination ofsecondary plant ingredients. An example which may be mentioned is theflow of latex in rubber trees. Under the influence of growth regulators,parthenocarpic fruits may be formed. Furthermore, it may be possible toinfluence the sex of the flowers. It is also possible to produce sterilepollen, which is of great importance in breeding and producing hybridseed.

By using growth regulators, branching of the plants can be controlled.On the one hand, by breaking the apical dominance, it is possible topromote the development of side shoots, which may be highly desirable inparticular in the cultivation of ornamental plants also in combinationwith an inhibition of growth. However, on the other hand it is alsopossible to inhibit the growth of the side shoots. This effect is ofparticular interest for example in the cultivation of tobacco or in thecultivation of tomatoes.

The amount of leaf on the plants can be controlled, under the influenceof growth regulators, so that defoliation of the plants at a desiredpoint in time is achieved. Such defoliation is of great importance inthe mechanical harvesting of cotton, but is also of interest forfacilitating harvesting in other crops, such as, for example, inviticulture. Defoliation of the plants can also be carried out to lowerthe transpiration of the plants before they are transplanted.

Growth regulators can also be used to regulate fruit dehiscence. On theone hand, it is possible to prevent premature fruit dehiscence. On theother hand, it is also possible to promote fruit dehiscence or evenflower abortion to achieve a desired mass (“thinning”) to breakalternation. Alternation is understood as the characteristic of somefruit species to deliver, owing to endogenous factors, highly varyingyields from year to year. Finally, using growth regulators at the timeof harvest, it is possible to reduce the forces required to detach thefruits to allow mechanical harvesting or to facilitate manualharvesting.

Growth regulators can furthermore be used to achieve faster or elsedelayed ripening of the harvested material before or after harvest. Thisis of particular advantage as this allows optimal adaptation to therequirements of the market. Furthermore, in some cases growth regulatorsmay improve the fruit coloration. In addition, growth regulators canalso be used to achieve maturation concentrated within a certain periodof time. This allows complete mechanical or manual harvesting in asingle operation, for example in the case of tobacco, tomatoes orcoffee.

By using growth regulators, it is furthermore possible to influence therest of seed or buds of the plants, so that plants such as, for example,pineapple or ornamental plants in nurseries, germinate, sprout or flowerat a point in time when they are normally not inclined to do so. Inareas where there is a risk of frost, it may be desirable to delaybudding or germination of seeds with the aid of growth regulators toavoid damage owing to late frosts.

Finally, growth regulators may induce resistance of the plants to frost,drought or high salinity of the soil. This allows the cultivation ofplants in regions which are normally unsuitable for this purpose.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) and/or the compositions according to the invention. Thepreferred ranges stated above for the active compounds or compositionsalso apply to the treatment of these plants.

Particular emphasis is given to the treatment of plants with thecompounds or compositions specifically mentioned in the present text.

The invention is illustrated by the examples below. However, theinvention is not limited to the examples.

PREPARATION EXAMPLES Preparation of Compound No. 11 (Process C)

Under an atmosphere of argon, a mixture of 2.0 g (7.4 mmol) of1-(4-bromophenoxy)-3,3-dimethylbutan-2-one and 1.35 g (8.5 mmol) of5-bromopyrimidine in 20 ml of dry tetrahydrofuran is cooled to −120° C.n-Butyllithium (3.54 ml, 2.5 M, 8.9 mmol) is then added slowly withstirring. After the addition has ended, the reaction mixture is slowlywarmed to room temperature overnight. 20 ml of a 10% strength ammoniumchloride solution are added to the reaction mixture, and the organicphase is removed. The organic phase is then washed with 1 N hydrochloricacid and saturated aqueous sodium chloride solution, dried over sodiumsulphate and filtered, and the filtrate is concentrated. The crudeproduct is then purified by column chromatography (cyclohexane/ethylacetate 1:1). This gives 1.89 g (73%) of the desired product.

Preparation of Compound No. 13 (Process B)

At room temperature and under an atmosphere of argon, 0.19 g (60%, 4.9mmol) of sodium hydride is added to 0.93 g (4.9 mmol) of4-bromothiophenol dissolved in 25 ml of N,N-dimethylformamide, and thereaction mixture is stirred at room temperature for 1 h. 0.8 g (4.5mmol) of 5-(2-tert-butyloxiran-2-yl)pyrimidine is then added, and thereaction mixture is stirred at 100° C. for 12 h. After cooling to roomtemperature, the solvent is removed under reduced pressure and saturatedaqueous sodium chloride solution and ethyl acetate are added to theresidue. The organic phase is separated off, dried over sodium sulphate,filtered and concentrated. The crude product is then purified by columnchromatography (cyclohexane/ethyl acetate 1:1). This gives 0.50 g (29%)of the desired product.

Preparation of 5-(2-tert-butyloxiran-2-yl)pyrimidine

Under an atmosphere of argon, 10 ml of dimethyl sulphoxide are slowlyadded dropwise to 0.96 g (4.3 mmol) of trimethylsulphoxonium iodide and0.17 g of sodium hydride (60%, 4.3 mmol). The reaction mixture is thenstirred at room temperature for 15 min, and 0.65 g (3.9 mmol) of2,2-dimethyl-1-(5-pyrimidinyl)-1-propanone, dissolved in 2 ml oftetrahydrofuran, is added. The reaction mixture is stirred at 50° C. for90 min. The reaction mixture is then concentrated under reducedpressure, and saturated aqueous sodium chloride solution and ethylacetate are added to the residue. The organic phase is separated off,dried over sodium sulphate, filtered and concentrated. This gives 0.70 g(99%) of the desired product, which is reacted without furtherpurification.

Preparation of Compound No. 21 (Process B)

At room temperature and under an atmosphere of argon, 78 mg (60%, 1.9mmol) of sodium hydride are added to 0.34 g (1.9 mmol) of 4-bromophenoldissolved in 15 ml of N,N-dimethylformamide, and the reaction mixture isstirred at room temperature for 1 h. 0.29 g (1.8 mmol) of5-(2-isopropyloxiran-2-yl)-pyrimidine is then added, and the reactionmixture is stirred at 100° C. for 12 h. After cooling to roomtemperature, the solvent is removed under reduced pressure and saturatedaqueous sodium chloride solution and ethyl acetate are added to theresidue. The organic phase is separated off, dried over sodium sulphate,filtered and concentrated. The crude product is then purified by columnchromatography (cyclohexane/ethyl acetate 1:1). This gives 82 mg (13%)of the desired product.

Preparation of 5-(2-isopropyloxiran-2-yl)pyrimidine

Under an atmosphere of argon, 50 ml of dimethyl sulphoxide are slowlyadded dropwise to 8.06 g (37 mmol) of trimethylsulphoxonium iodide and1.47 g of sodium hydride (60%, 37 mmol). The reaction mixture is thenstirred at room temperature for 15 min, and 5.00 g (33 mmol) of2-methyl-1-(5-pyrimidinyl)-1-propanone, dissolved in 10 ml oftetrahydrofuran, are added. The reaction mixture is stirred at 50° C.for 90 min. The reaction mixture is then concentrated under reducedpressure, and saturated aqueous sodium chloride solution and ethylacetate are added to the residue. The organic phase is separated off,dried over sodium sulphate, filtered and concentrated. This gives 1.36 g(25%) of the desired product, which is reacted without furtherpurification.

Preparation of Compound No. 3 (Process B)

At room temperature and under an atmosphere of argon, 68 mg (60%, 1.7mmol) of sodium hydride are added to 0.40 g (1.7 mmol) of4-iodothiophenol dissolved in 15 ml of N,N-dimethylformamide, and thereaction mixture is stirred at room temperature for 1 h. 0.28 g (1.5mmol) of 1-[[2-(1,1-dimethylethyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole(preparation see DE 3111238) is then added, and the reaction mixture isstirred at 100° C. for 12 h. After cooling to room temperature, thesolvent is removed under reduced pressure and saturated aqueous sodiumchloride solution and ethyl acetate are added to the residue. Theorganic phase is separated off, dried over sodium sulphate, filtered andconcentrated. The crude product is then purified by columnchromatography (cyclohexane/ethyl acetate 1:1). This gives 0.27 g (41%)of the desired product.

Analogously to the above examples and in accordance with the generaldescriptions of the processes according to the invention, it is possibleto obtain the compounds of the formula (I) listed in Table 1 below.

TABLE 1 (I)

No. X Y Z R Physical data 1 1H-1,2,4-triazol-1-ylmethyl O 4-I ^(t)Bu¹H-NMR (400 MHz, DMSO-d₆): δ = 1.02 (s, 9H), 3.57 (d, J = 10 Hz, 1H),3.88 (d, J = 10 Hz, 1H), 4.36 (d, J = 14 Hz, 1H), 4.56 (d, J = 14 Hz,1H), 4.66 (s, 1H), 6.71 (m, 2H), 7.56 (m, 2H), 7.84 (s, 1H), 8.34 (s,1H) ppm. 2 1H-1,2,4-triazol-1-ylmethyl S 4-Br ^(t)Bu 31H-1,2,4-triazol-1-ylmethyl S 4-I ^(t)Bu ¹H-NMR (400 MHz, DMSO-d₆): δ =0.96 (s, 9H), 3.11-3.21 (m, 2H), 4.38-4.41 (m, 2H), 4.72 (s, 1H), 7.06(dd, J = 6 Hz, 2 Hz, 2H), 7.58 (dd, J = 6 Hz, 2 Hz, 2H), 7.89 (s, 1H),8.42 (s, 1H) ppm. 4 1H-1,2,4-triazol-1-ylmethyl SO 4-Br ^(t)Bu 51H-1,2,4-triazol-1-ylmethyl SO 4-I ^(t)Bu 6 1H-1,2,4-triazol-1-ylmethylSO₂ 4-Br ^(t)Bu 7 1H-1,2,4-triazol-1-ylmethyl SO₂ 4-I ^(t)Bu 81H-1,2,4-triazol-1-ylmethyl CH₂ 4-I ^(t)Bu 9 1H-1,2,4-triazol-1-ylmethylO 4-Br 1-Me-cPr ¹H-NMR (400 MHz, DMSO-d₆): δ = −0.17 (m, 1H), 0.03 (m,1H), 0.24 (m, 1H), 0.65 (m, 1H), 1.1 (s, 1H), 3.9 (d, 1H), 4.0 (d, 1H),4.48 (dd, 2H), 4.9 (s, 1H), 6.9 (dd, 2H), 7.4 (dd, 2H), 7.9 (s, 1H), 8.4(s, 1H) ppm. 10 1H-1,2,4-triazol-1-ylmethyl O 4-I 1-Me-cPr ¹H-NMR (400MHz, DMSO-d₆): δ = −0.17 (m, 1H), 0.02 (m, 1H), 0.21 (m, 1H), 0.64 (m,1H), 1.1 (s, 1H), 3.9 (d, 1H), 4.0 (d, 1H), 4.48 (dd, 2H), 4.9 (s, 1H),6.8 (dd, 2H), 7.6 (dd, 2H), 7.9 (s, 1H), 8.4 (s, 1H) ppm. 11pyrimidin-5-yl O 4-Br ^(t)Bu ¹H-NMR (400 MHz, DMSO-d₆): δ = 0.93 (s,9H), 4.22 (d, J = 10 Hz, 1H), 4.76 (d, J = 10 Hz, 1H), 5.32 (s, 1H),6.89 (dd, J = 10 Hz, 2 Hz, 2H), 7.39 (dd, J = 10 Hz, 2 Hz, 2H), 8.80 (s,2H), 9.01 (s, 1H) ppm. 12 pyrimidin-5-yl O 4-I ^(t)Bu ¹H-NMR (400 MHz,DMSO-d⁶): δ = 0.91 (s, 9H), 4.20 (d, J = 10 Hz, 1H), 4.79 (d, J = 10 Hz,1H), 5.50 (s, 1H), 6.77 (dd, J = 7 Hz, 2 Hz, 2H), 7.55 (dd, J = 7 Hz, 2Hz, 2H), 8.80 (s, 2H), 9.03 (s, 1H) ppm. 13 pyrimidin-5-yl S 4-Br ^(t)Bu¹H-NMR (400 MHz, DMSO-d₆): δ = 0.91 (s, 9H), 3.47 (d, J = 12 Hz, 1H),4.05 (d, J = 12 Hz, 1H), 5.49 (s, 1H), 7.27 (m, 2H), 7.44 (m, 2H), 8.80(s, 2H), 9.03 (s, 1H) ppm. 14 pyrimidin-5-yl S 4-I ^(t)Bu 15pyrimidin-5-yl SO 4-Br ^(t)Bu 16 pyrimidin-5-yl SO 4-I ^(t)Bu 17pyrimidin-5-yl SO₂ 4-Br ^(t)Bu 18 pyrimidin-5-yl SO₂ 4-I ^(t)Bu 19pyrimidin-5-yl CH₂ 4-Br ^(t)Bu 20 pyrimidin-5-yl CH₂ 4-I ^(t)Bu 21pyrimidin-5-yl O 4-Br ^(i)Pr ¹H-NMR (400 MHz, DMSO-d₆): δ = 0.70 (d, J =7 Hz, 3H), 0.93 (d, J = 7 Hz, 3H), 2.27 (sept, J = 7 Hz, 1H), 4.11 (d, J= 10 Hz, 1H), 4.36 (d, J = 10 Hz, 1H), 5.52 (s, 1H), 6.89 (dd, J = 7 Hz,2 Hz, 2H), 7.41 (dd, J = 7 Hz, 2 Hz, 2H), 8.88 (s, 2H), 9.05 (s, 1H)ppm. 22 pyrimidin-5-yl O 4-I ^(i)Pr ¹H-NMR (400 MHz, DMSO-d₆): δ = 0.69(d, J = 7 Hz, 3H), 0.93 (d, J = 7 Hz, 3H), 2.27 (sept, J = 7 Hz, 1H),4.10 (d, J = 10 Hz, 1H), 4.34 (d, J = 10 Hz, 1H), 5.52 (s, 1H), 6.76(dd, J = 9 Hz, 3 Hz, 2H), 7.55 (dd, J = 9 Hz, 3 Hz, 2H), 8.88 (s, 2H),9.05 (s, 1H) ppm. 23 pyrimidin-5-yl O 4-Br 1-F-cPr ¹H-NMR (400 MHz,DMSO-d₆): δ = 0.9- 1.25 (m, 4H), 4.35 (s, 1H), 4.41 (dd, J = 10 Hz, 2Hz,1H), 4.54 (dd, J = 10 Hz, 2 Hz, 1H), 6.90 (dd, J = 7 Hz, 2 Hz, 2H), 7.43(dd, J = 7 Hz, 2 Hz, 2H), 8.95 (s, 2H), 9.11 (s, 1H) ppm. 24pyridin-3-yl O 4-I ^(t)Bu 25 pyridin-3-yl S 4-I ^(t)Bu 26 pyridin-3-ylSO 4-Br ^(t)Bu 27 pyridin-3-yl SO 4-I ^(t)Bu 28 pyridin-3-yl SO₂ 4-Br^(t)Bu 29 pyridin-3-yl SO₂ 4-I ^(t)Bu 30 pyridin-3-yl CH₂ 4-Br ^(t)Bu¹H-NMR (400 MHz, DMSO-d₆): δ = 0.84 (s, 9H), 1.91-2.00 (m, 2H),2.45-2.58 (m, 2H), 4.92 (s, 1H), 7.16 (d, J = 8Hz, 2H), 7.37 (bs, 1H),7.44 (d, J = 8 Hz, 2H), 7.83 (d, 1H), 8.73 (bs, 1H), 8.68 (bs, 1H) ppm31 pyridin-3-yl CH₂ 4-I ^(t)Bu 32 pyridin-3-yl O 4-Br 1-F-cPr ¹H-NMR(400 MHz, DMSO-d₆): δ = 0.75- 1.25 (m, 4H), 4.21 (s, 1H), 4.41 (dd, J =10 Hz, 2Hz, 1H) 4.51 (dd, J = 10 Hz, 2 Hz, 1H), 6.90 (d, J = 9 Hz, 2H),7.36 (dd, 1H), 7.42 (d, J = 9 Hz, 2H), 7.96 (dd, 1H), 8.52 (dd, 1H),8.80 (s, 1H) ppm. 33 pyrimidin-5-yl O 3-Br ^(t)Bu 1H-NMR (400 MHz,DMSO-d6): δ = 0.91 (s, 9H), 4.22 (d, J = 10 Hz, 1H), 4.86 (d, J = 10 Hz,1H), 5.50 (s, 1H), 6.90 (m, 1H), 7.11 (m, 1H), 7.21 (m, 2H), 8.21 (s,2H), 9.04 (s, 1H) ppm. 34 pyrimidin-5-yl O 3-I ^(i)Pr 1H-NMR (400 MHz,DMSO-d6): δ = 0.70 (d, J = 7 Hz, 3H), 0.93 (d, J = 7 Hz, 3H), 2.26 (m,1H), 4.12 (d, J = 10 Hz, 1H), 4.37 (d, J = 10 Hz, 1H), 5.51 (s, 1H),6.92 (m, 1H), 7.04 (m, 1H), 7.30 (m, 2H), 8.88 (s, 2H), 9.06 (s, 1H)ppm. 35 pyrimidin-5-yl O 3-Br 1-F-cPr ¹H-NMR (600 MHz, DMSO-d₆): δ =0.82- 1.25 (m, 4H), 4.43 (d, J = 10 Hz, 1H), 4.53 (s, 1H, OH), 4.55 (d,J = 10 Hz, 1H), 6.93 (dd, J = 8 Hz, 2 Hz, 1H), 6.90 (dd, J = 7 Hz, 2 Hz,2H), 7.13-7.22 (m, 3H), 8.96 (s, 2H), 9.11 (s, 1H) ppm. 36 pyridin-3-ylO 3-Br 1-F-cPr ¹H-NMR (600 MHz, DMSO-d6): δ = 0.80-1.22 (m, 4H), 4.18(s, 1H), 4.43 (d, J = 10 Hz, 1H), 4.52 (d, J = 10 Hz, 1H), 6.94 (dd, J =8 Hz, J = 8 Hz, 2H), 7.13-7.23 (m, 3H), 7.36 (dd, J = 8 Hz, 4.5 Hz, 1H),7.96 (d, J = 8 Hz, 1H), 8.53 (dd, J = 5 Hz, 1.3 Hz, 1H), 8.80 (s, 1H)ppm. 37 pyrimidin-5-yl O 4-I 1-F-cPr ¹H-NMR (600 MHz, DMSO-d₆): δ =0.81- 1.26 (m, 4H), 4.40 (s, 1H, OH), 4.41 (d, J = 8 Hz, 1H), 4.53 (d, J= 8 Hz, 1H), 6.89 (d, J = 9 Hz, 2H), 7.42 (d, J = 9 Hz, 2H), 8.95 (s,2H), 9.10 (s, 1H) ppm. 38 1H-1,2,4-triazol-1-ylmethyl O 3-Br ^(t)Bu¹H-NMR (400 MHz, DMSO-d₆): δ = 1.02 (s, 9H), 3.57 (d, 1H), 3.88 (d, 1H),4.36 (d, 1H), 4.56 (d, 1H), 4.9 (s, 1H), 6.85 (dd, 1H), 7.05 (brs, 1H),7.15 (d, 1H), 7.25 (t, 1H), 7.9 (s, 1H), 8.4 (s 1H), ppm. 391H-1,2,4-triazol-1-ylmethyl O 3-Br 1-Me-cPr ¹H-NMR (400 MHz, DMSO-d₆): δ= −0.2 to −0.14 (m, 1H), 0.01-0.04 (m, 1H), 0.22- 0.25 (m, 1H), 0.6-0.65(m, 1H) 1.1 (s, 3H), 3.9 (d, 1H), 4.1 (d, 1H), 4.45 (ABq, 2H), 4.9 (s,1H), 6.95 (dd, 1H), 7.0-7.2(m, 2H), 7.25 (t, 1H), 7.9 (s, 1H) 8.4 (s,1H) ppm. 40 1H-1,2,4-triazol-1-ylmethyl O 3-I ^(t)Bu ¹H-NMR (400 MHz,DMSO-d₆): δ = 1.02 (s, 9H), 3.55 (d, 1H), 3.9 (d, 1H), 4.4 (d, 1H), 4.6(d, 1H), 4.8 (brs, 1H), 6.9 (dd, 1H), 7.1 (t, 1H), 7.2 (brs, 1H), 7.3(d, 1H), 7.9 (s, 1H), 8.4 (s 1H), ppm. 41 1H-1,2,4-triazol-1-ylmethyl O3-I 1-Me-cPr ¹H-NMR (400 MHz, DMSO-d₆): δ = −0.2 to −0.14 (m, 1H),0.01-0.04 (m, 1H), 0.22- 0.25 (m, 1H), 0.6-0.65 (m, 1H) 1.1 (s, 3H), 3.9(d, 1H), 4.05 (d, 1H), 4.45 (ABq, 2H), 4.9 (s, 1H), 7.0 (dd, 1H), 7.1(t,1H), 7.25- 7.35 (m, 2H), 7.9 (s, 1H) 8.4 (s, 1H) ppm. 421H-1,2,4-triazol-1-ylmethyl O 2-Br 1-Me-cPr ¹H-NMR (400 MHz, DMSO-d₆): δ= −0.2 to −0.14 (m, 1H), 0.01-0.04 (m, 1H), 0.29 0.35 (m, 1H), 0.68-0.75(m, 1H) 1.2 (s, 3H), 3.95 (d, 1H), 4.05 (d, 1H), 4.55 (ABq, 2H), 6.9 (t,1H), 7.1 (d, 1H), 7.35 (t, 1H),7.6 (d, 1H), 7.9 (s, 1H) 8.4 (s, 1H) ppm.43 1H-1,2,4-triazol-1-ylmethyl O 2-I ^(t)Bu ¹H-NMR (400 MHz, DMSO-d₆): δ= 1.1 (s, 9H), 3.5 (d, 1H), 4.0 (d, 1H), 4.45 (d, 1H), 4.75 (d, 1H), 4.8(brs, 1H), 6.8 (t, 1H), 6.9 (d, 1H), 7.45 (t, 1H), 7.8 (d, 1H), 7.95 (s,1H), 8.35 (s 1H), ppm. 44 1H-1,2,4-triazol-1-ylmethyl O 2-I 1-Me-cPr¹H-NMR (400 MHz, DMSO-d₆): δ = −0.2 to −0.14 (m, 1H), 0.01-0.04 (m, 1H),0.29-0.32 (m, 1H), 0.71-0.75 (m, 1H) 1.2 (s, 3H), 3.95 (d, 1H), 4.05 (d,1H), 4.55 (d, 1H), 4.65 (d, 1H), 4.9 (s, 1H), 6.7-6.9 (m, 1H), 7.0 (d,1H), 7.3-7.4 (m, 1H), 7.8 (d, 1H) 7.9 (s 1H), 8.4 (s, 1H) ppm. 451H-1,2,4-triazol-1-ylmethyl O 2-Br ^(t)Bu ¹H-NMR (400 MHz, DMSO-d₆): δ =1.1 (s, 9H), 3.5 (d, 1H), 3.95 (d, 1H), 4.45 (d, 1H), 4.65 (d, 1H), 4.8(s, 1H), 6.9 (t, 1H), 6.95 (d, 1H), 7.3 (t, 1H), 7.6 (d, 1H), 7.85 (s,1H), 8.4 (s 1H), ppm. 46 1H-1,2,4-triazol-1-ylmethyl S 3-Br ^(t)Bu¹H-NMR (400 MHz, DMSO-d₆): δ = 0.95 (s, 9H), 4.4 (ABq, 2H), 4.95 (brs,1H), 7.2- 7.35 (m, 3H), 7.5 (brs, 1H), 7.95 (s, 1H), 8.5 (s 1H), ppm.One CH₂ group is at 3.3 ppm under the DMSO peak.. 471H-1,2,4-triazol-1-ylmethyl S 2-Br ^(t)Bu ¹H-NMR (400 MHz, DMSO-d₆): δ =1.0 (s, 9H), 4.45 (ABq, 2H), 5.0 (brs, 1H), 7.1 (t, 1H), 7.25-7.35 (m,2H), 7.6 (d, 1H), 7.9 (s 1H), 8.5 (s 1H), ppm. One CH₂ group is at 3.3ppm under the DMSO peak.. 48 1H-1,2,4-triazol-1-ylmethyl S 3-Br 1-Me-cPr¹H-NMR (400 MHz, DMSO-d₆): δ = −0.2 to −0.16 (m, 1H), 0.01-0.05 (m, 1H),0.15-0.18 (m, 1H), 0.71-0.75 (m, 1H) 1.1 (s, 3H), 3.2 (d, 1H), 3.45 (d,1H), 4.45 (ABq, 2H), 4.9 (s, 1H), 7.25 (dd, 1H), 7.3-7.4 (m, 2H), 7.5(s, 1H) 7.95 (s 1H), 8.4 (s, 1H) ppm. 49 1H-1,2,4-triazol-1-ylmethyl S2-Br 1-Me-cPr ¹H-NMR (400 MHz, DMSO-d₆): δ = −0.2 to −0.16 (m, 1H),0.01-0.05 (m, 1H), 0.15-0.18 (m, 1H), 0.73-0.8 (m, 1H) 1.1 (s, 3H), 3.15(d, 1H), 3.4 (d, 1H), 4.4 (ABq, 2H), 5.0 (s, 1H), 7.0-7.15 (m, 1H),7.3-7.4 (m, 2H), 7.6 (d, 1H) 7.95 (s 1H), 8.45 (s, 1H) ppm. 501H-1,2,4-triazol-1-ylmethyl S 2-Br 1-Cl-cPr ¹H-NMR (400 MHz, DMSO-d₆): δ= 0.60- 0.7 (m, 2H), 0.85-0.92 (m, 1H), 1.2-1.35 (m, 1H) 3.35 (d, 1H),3.6 (d, 1H), 4.60 (ABq, 2H), 5.7 (s, 1H), 7.0-7.17 (m, 1H), 7.3-7.41 (m,2H), 7.6 (d, 1H) 7.95 (s 1H), 8.45 (s, 1H) ppm. 511H-1,2,4-triazol-1-ylmethyl S 3-Br 1-Cl-cPr ¹H-NMR (400 MHz, DMSO-d₆): δ= 0.60- 0.7 (m, 2H), 0.83-0.91 (m, 1H), 1.2-1.33 (m, 1H) 3.39 (d, 1H),3.65 (d, 1H), 4.55 (ABq, 2H), 5.65 (s, 1H), 7.25 (t, 1H), 7.33- 7.43 (m,2H), 7.55 (s, 1H) 8.0 (s 1H), 8.4 (s, 1H) ppm.

USE EXAMPLES Example A Sphaerotheca Test (Cucumber)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young cucumber plantsare sprayed with the preparation of active compound at the statedapplication rate. 1 day after the treatment, the plants are inoculatedwith a spore suspension of Sphaerotheca fuliginea. The plants are thenplaced in a greenhouse at a relative atmospheric humidity of 70% and atemperature of 23° C. Evaluation is carried out 7 days after theinoculation. 0% means an efficacy which corresponds to that of thecontrol, whereas an efficacy of 100% means that no infection isobserved.

In this test, the following compounds according to the invention 1, 2,3, 4, 9, 10, 11, 12, 13, 21, 22, 23, 30, 32, 33, 35, 36 and 37 show, atan active compound concentration of 500 ppm, an efficacy of 70% or more.

Example B Leptosphaeria Nodorum Test (Wheat)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young wheat plants aresprayed with the preparation of active compound at the statedapplication rate. 1 day after the treatment, the plants are inoculatedwith an aqueous spore suspension of Leptosphaeria nodorum and thenremain at 100% relative atmospheric humidity and 22° C. for 48 h. Theplants are then placed in a greenhouse at 90% relative atmospherichumidity and a temperature of 22° C. Evaluation is carried out 7-9 daysafter the inoculation. 0% means an efficacy which corresponds to that ofthe control, whereas an efficacy of 100% means that no infection isobserved.

In this test, the following compounds according to the invention 1, 2,3, 10, 11, 12, 13, 21, 22, 23, 30, 32, 33, 35, 36 and 37 show, at anactive compound concentration of 500 ppm, an efficacy of 70% or more.

Example C Alternaria Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier:   1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Alternaria solani. The plants are thenplaced in an incubation cabin at about 20° C. and 100% relativeatmospheric humidity. Evaluation is carried out 3 days after theinoculation. 0% means an efficacy which corresponds to that of thecontrol, whereas an efficacy of 100% means that no infection isobserved.

Results: Alternaria test (tomato)/protective Active compound applicationEfficacy Active compounds rate in ppm in % known from EP-A 0 040 345,Example I-1:

100 45 known from EP-A 0 028 755, Example 1:

100 75 according to the invention, Example 1:

100 94 according to the invention, Example 11:

100 99

Furthermore, in this test, the following compounds according to theinvention 2, 3, 10, 9, 23, 22, 12, 33 and 37 show, at an active compoundconcentration of 100 ppm, an efficacy of 70% or more.

Example D Pyrenophora Teres Test (Barley)/Protective

Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, the plants are sprayed with aspore suspension of Pyrenophora teres. The plants remain in anincubation cabin at 20° C. and a relative atmospheric humidity of 100%for 48 hours. The plants are placed in a greenhouse at a temperature ofabout 20° C. and a relative atmospheric humidity of about 80%.Evaluation is carried out 8 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

Results: Pyrenophora teres test (barley)/protective Active compoundapplication Efficacy Active compounds rate in ppm in % known from EP-A 040 345, Example I-1:

1000 57 known from EP-A 0 028 755, Example 1:

500 93 according to the invention, Example 1:

1000 86 according to the invention, Example 11:

500 100

Example E Venturia Test (Apple)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier:   1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the apple scab pathogen Venturiainaequalis and then remain in an incubation cabin at about 20° C. and100% relative atmospheric humidity for 1 day. The plants are then placedin a greenhouse at about 21° C. and a relative atmospheric humidity ofabout 90%. Evaluation is carried out 10 days after the inoculation. 0%means an efficacy which corresponds to that of the control, whereas anefficacy of 100% means that no infection is observed.

In this test, the following compounds according to the invention 1, 2,3, 9, 10, 11, 12, 22, 23 and 37 show, at an active compoundconcentration of 100 ppm, an efficacy of 70% or more.

Example F Blumeria Graminis Test (Barley)/Protective

Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, the plants are dusted with sporesof Blumeria graminis f.sp. hordei. The plants are placed in a greenhouseat a temperature of about 18° C. and a relative atmospheric humidity ofabout 80% to promote the development of mildew pustules. Evaluation iscarried out 7 days after the inoculation. 0% means an efficacy whichcorresponds to that of the control, whereas an efficacy of 100% meansthat no infection is observed.

In this test, the following compounds according to the invention 1, 2,3, 9, 10, 11, 12, 22 and 33 show, at an active compound concentration of500 ppm, an efficacy of 70% or more.

Example G Puccinia Triticina Test (Wheat)/Protective

Solvent: 49 parts by weight of N,N-dimethylacetamide Emulsifier:  1 partby weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, the plants are sprayed with aspore suspension of Puccinia triticina. The plants remain in anincubation cabin at 20° C. and a relative atmospheric humidity of 100%for 48 hours. The plants are placed in a greenhouse at a temperature ofabout 20° C. and a relative atmospheric humidity of about 80%.Evaluation is carried out 8 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, the following compounds according to the invention 1, 2,3, 9, 10, 11, 12 and 22 show, at an active compound concentration of1000 ppm, an efficacy of 70% or more.

Example H Production of Fumonisin FB1 by Fusarium proliferatum

The compounds were tested in microtitre plates in a fumonisin-inducingliquid medium (0.5 g of malt extract, 1 g of yeast extract, 1 g ofbactopeptone, 20 g of fructose, 1 g of KH₂PO₄, 0.3 g of MgSO₄×7H₂O, 0.3g of KCl, 0.05 g of ZnSO₄×7H₂O and 0.01 g of CuSO₄×5H₂O per litre) withDMSO (0.5%). Inoculation was carried out using a concentrated sporesuspension of Fusarium proliferatum at a final concentration of 2000spores/ml. The plate was incubated at 20° C. and high atmospherichumidity for 5 days. At the beginning and after 5 days, the OD wasmeasured at OD620 (repeated measurements: 3×3 measurements per well) tocalculate the inhibition of growth. After 5 days, a sample of the liquidmedium was removed and diluted 1:1000 with 50% strength acetonitrile.The concentration of FB1 of the diluted samples was analyzed byHPLC-MS/MS, and the measured values were used to calculate theinhibition of fumonisin FB1 production compared to an activecompound-free control.

HPLC-MS/MS was carried out using the following parameters:

ionization: ESI positiveion spray voltage: 5500 Vspray gas temperature: 500° C.decluster potential: 114 Vcollision energy: 51 eVcollision gas: N₂NMR trace: 722.3>352.3; dwell time 100 msHPLC column: Waters Atlantis T3 (trifunctionally C18-bonded, sealed)particle size: 3 μmcolumn dimensions: 50×2 mmtemperature: 40° C.solvent A: water+0.1% HCOOH (v/v)solvent B: acetonitrile+0.1% HCOOH (v/v)flow rate 400 μl/minuteinjection volume: 5 μlgradient:

Time [min] A % B % 0 90 10 2 5 95 4 5 95 4.1 90 10 9 90 10

Examples of the Inhibition of Fumonisin FB1 Production

Examples Nos. 1, 3, 9, 10, 11, 12, 13, 21, 22, 23 and 32 showed anactivity of >80% for the inhibition of fumonisin FB1 production at aconcentration of 50 μM. The inhibition of growth of Fusariumproliferatum of the examples mentioned varied from 36 to 100% at 50 μM.

Example I Production of Don/acetyl-Don by Fusarium graminearum

The compounds were tested in microtitre plates in a DON-inducing liquidmedium (1 g of (NH₄)₂HPO₄, 0.2 g of MgSO₄×7H₂O, 3 g of KH₂PO₄, 10 g ofglycerol, 5 g of NaCl and 40 g of sucrose per litre) and DMSO (0.5%).Inoculation was carried out using a concentrated spore suspension ofFusarium graminearum at a final concentration of 2000 spores/ml. Theplate was incubated at 28° C. and high atmospheric humidity for 7 days.At the beginning and after 3 days, the OD was measured at OD620(repeated measurements: 3×3 measurements per well) to calculate theinhibition of growth. After 7 days, 1 volume of an 84/16acetonitrile/water mixture was added, and a sample of the liquid mediumfrom each well was then removed and diluted 1:100 in 10% strengthacetonitrile. The proportions of DON and acetyl-DON of the samples wereanalyzed by HPLC-MS/MS, and the measured values were used to calculatethe inhibition of DON/AcDON production compared to an activecompound-free control.

HPLC-MS/MS measurements were carried out using the following parameters:

ionization: ESI negativeion spray voltage: −4500 Vspray gas temperature: 500° C.decluster potential: −40 Vcollision energy: −22 eVcollision gas: N₂NMR trace: 355.0>264.9HPLC column: Waters Atlantis T3 (trifunctionally C18-bonded, sealed)particle size: 3 μmcolumn dimensions: 50×2 mmtemperature: 40° C.solvent A: water/2.5 mM NH₄OAc+0.05% CH₃COOH (v/v)solvent B: methanol/2.5 mM NH₄OAc+0.05% CH₃COOH (v/v)flow rate: 400 μl/minuteinjection volume: 11 μlgradient:

Time [min] A % B % 0 100 0 0.75 100 0 1.5 5 95 4 5 95 5 100 0 10 100 0

Examples of DON Inhibition

Examples Nos. 1, 3, 9, 10, 11, 12, 21, 22 and 32 showed an activityof >80% for the inhibition of DON/AcDON production at 50 μM. Theinhibition of growth of Fusarium graminearum of the examples mentionedvaried from 34 to 99% at 50 μM.

Example J Production of Aflatoxins by Aspergillus parasiticus

The compounds were tested in microtitre plates (black 96-well plateswith flat and transparent bottom) in an aflatoxin-inducing liquid medium(20 g of sucrose, 4 g of yeast extract, 1 g of KH₂PO₄ and 0.5 g ofMgSO₄×7H₂O per litre), with 20 mM Cavasol(hydroxypropyl-beta-cyclodextrin) and 1% DMSO added. Inoculation wascarried out using a concentrated spore suspension of Aspergillusparasiticus at a final concentration of 1000 spores/ml. The plate wasincubated at 20° C. and high atmospheric humidity for 7 days. After 7days, the OD was measured at OD620 (repeated measurements: 4×4measurements per well) to calculate the inhibition of growth. At thesame time, across the bottom of the plate the fluorescence was measuredat Em_(360nm) and EX_(426nm) (repeated measurements: 3×3 measurementsper well) to calculate the inhibition of aflatoxin production comparedto an active compound-free control.

Examples of an Inhibition of Aflatoxin Production

Examples Nos. 11 and 32 showed, at 50 μM, an activity of >80% inhibitionof aflatoxin production. The inhibition of the growth of Aspergillusparasiticus at 50 μM by these examples varied in the range from 43 to69%.

Example K Phytoregulatory Pre- and Post-Emergence Action PhytoregulatoryPre-Emergence Action

Seeds of monocotyledonous or dicotyledonous crop plants are placed inwood-fibre pots in sandy loam and covered with soil. The test compounds,formulated in the form of wettable powders (WP), are then, as an aqueoussuspension with a water application rate of 600 l/ha (converted), with0.2% of wetting agent added, applied at various dosages to the surfaceof the covering soil. After the treatment, the pots are placed in agreenhouse and kept under good growth conditions for the test plants.The visual assessment of the suppression of growth in the test plants iscarried out after a trial period of about 3 weeks by comparison withuntreated controls (phytoregulatory activity in percent: 100%activity=maximum inhibition of plant growth, 0% activity=plant growthlike that of an untreated control.)

Phytoregulatory Post-Emergence Action

Seeds of monocotyledonous and dicotyledonous crop plants are placed insandy loam in wood-fibre pots, covered with soil and cultivated in agreenhouse under good growth conditions. 2 to 3 weeks after sowing, thetest plants are treated at the one-leaf stage. The test compounds,formulated as wettable powders (WP), are, with a water application rateof 600 l/ha (converted), with 0.2% of wetting agent added, sprayed atvarious dosages onto the green parts of the plants. After the testplants have been kept in the greenhouse under optimum growth conditionsfor about 3 weeks, the activity of the preparations is rated visually incomparison to untreated controls (phytoregulatory activity in percent:100% activity=maximum inhibition of plant growth, 0% activity=plantgrowth like that of an untreated control.)

Results: Phytoregulatory pre- and post-emergence action Post- Inhibitionof the emergence growth of useful or dosage harmful plants in % Activecompounds [g of a.i./ha] SETVI TRZAS BRSNW known from EP-A 0 028 755,Example 1:

80 50 50 60 according to the invention, Example 11:

80 70 70 60 SETVI = Setaria viridis (green foxtail), TRZAS = Triticumaestivum (common wheat), BRSNW = Brassica napus (rape).

Inhibition of the growth of useful or Pre-emergence harmful plants in %Active compounds dosage [g of a.i./ha] ORYSA BRSNW known from EP-A 0 028755, Example 1:

80 40 70 according to the invention, Example 11:

80 60 80 BRSNW = Brassica napus (rape), ORYSA = Oryza sativa (rice).

1. Phenyl(oxy/thio)alkanol compounds of formula (I)

in which: X represents 5-pyrimidinyl, 1H-1,2,4-triazol-1-ylmethyl,3-pyridinyl, 1H-1,3-imidazol-1-ylmethyl or2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl, Y represents O, S, SO,SO₂ or CH₂, Z represents bromine or iodine, R represents tert-butyl,isopropyl, 1-halocyclopropyl, 1-(C₁-C₄-alkyl)cyclopropyl,1-(C₁-C₄-alkoxy)cyclopropyl or 1-(C₁-C₄-alkylthio)cyclopropyl, and theagrochemically active salts thereof, except for the compounds1-(4-bromophenoxy)-3,3-dimethyl-2-(pyridin-3-yl)butan-2-ol,1-(4-bromophenylthio)-3,3-dimethyl-2-(pyridin-3-yl)butan-2-ol,1-(4-bromophenylthio)-3-methyl-2-(pyridin-3-yl)butan-2-ol,2-(4-bromophenoxy)-1-(1-chlorocyclopropyl)-1-(pyridin-3-yl)ethanol,1-(4-bromophenoxy)-3,3-dimethyl-2-(1H-1,2,4-triazol-1-ylmethyl)butan-2-ol,1-(4-bromophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol,4-(4-bromophenyl)-2-(1-methylcyclopropyl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol,4-(4-bromophenyl)-2-(1-chlorocyclopropyl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol.2. Phenyl(oxy/thio)alkanol compounds of formula (I) according to claim 1in which: X represents 5-pyrimidinyl, 1H-1,2,4-triazol-1-ylmethyl,3-pyridinyl or 2,4-dihydro-3H-1,2,4-triazole-3-thion-1-ylmethyl, Yrepresents O, S or CH₂, Z represents bromine or iodine which is locatedin position 4, and R represents tert-butyl, isopropyl,1-chlorocyclopropyl, 1-methylcyclopropyl, 1-methoxycyclopropyl or1-methylthiocyclopropyl.
 3. Compounds of claim 1 having formula (I-a)

in which Y, Z and R have the meanings given in claim
 1. 4. Compounds ofclaim 1 having formula (I-c)

in which Y, Z and R have the meanings given in claim
 1. 5. Compounds ofthe formula (I-e)

in which Y, Z and R have the meanings given in claim
 1. 6. Method forcontrolling phytopathogenic harmful fungi, characterized in thatphenyl(oxy/thio)alkanol derivatives of the formula (I) according toclaim 1 are applied to the phytopathogenic harmful fungi, their habitator a combination thereof.
 7. Composition for controlling phytopathogenicharmful fungi, characterized in that it comprises at least one ofphenyl(oxy/thio)alkanol derivatives of the formula (I) according toclaim 1, and an extender, a surfactant, or combinations thereof. 8.(canceled)
 9. Process for preparing compositions for controllingphytopathogenic harmful fungi, characterized in thatphenyl(oxy/thio)alkanol derivatives of the formula (I) according toclaim 1 are mixed with an extender, a surfactant, or combinationsthereof.
 10. Process for preparing phenyl(oxy/thio)alkanol derivativesof the formula (I) according to claim 1, characterized in that (A) if Xrepresents 1-H-1,2,4-triazol-1-ylmethyl or 1H-1,3-imidazol-1-ylmethyl,oxirane derivatives of the formula (II)

in which Y, Z and R have the meanings given in claim 1, are reacted with1,2,4-triazole or 1,3-imidazole of the formula (III)

in which A represents CH or N, in the presence of a diluent; or (B) if Xrepresents 1H-1,2,4-triazol-1-ylmethyl, 1H-1,3-imidazol-1-ylmethyl,5-pyrimidinyl or 3-pyridinyl, reacting oxirane derivatives of theformula (IV)

in which R has the meanings given in claim 1, and X² is1H-1,2,4-triazol-1-ylmethyl, 1H-1,3-imidazol-1-ylmethyl, 5-pyrimidinylor 3pyridinyl, are reacted with a (thio)phenol of the formula (V)

in which Y and Z have the meanings given in claim 1, in the presence ofa diluent; or (C) if X represents 5-pyrimidinyl or 3-pyridinyl,phenyl(oxy/thio)ketones of the formula (VI)

in which Y, Z and R have the meanings given in claim 1, and X³ is5-pyrimidinyl or 3-pyridinyl, are reacted with a halide of the formula(VII)Hal-X³  (VII) in which Hal represents halogen, in the presence of adiluent and in the presence of an organic alkali metal compound; or (D)if X represents 5-pyrimidinyl or 3-pyridinyl, in a first step, bromidesof the formula (VIII)

in which X⁴ is 5-pyrimidinyl or 3-pyridinyl, are reacted with a(thio)phenol of the formula (V)

in which Y and Z have the meanings given in claim 1, in the presence ofa diluent, and the phenyl(oxy/thio)ketones of the formula (IX) obtainedin this manner

in which Y and Z have the meanings given in claim 1, and X⁴ is5-pyrimidinyl or 3-pyridinyl are reacted in a second step withorganometal compounds of the formula(X)R-M  (X) in which R has the meanings given in claim 1 and M representsmetal, in the presence of a diluent and in the presence of an organicalkali metal compound; or (E) phenyl(oxy/thio)alkanol derivatives of theformula (I-c)

in which Y, Z and R have the meanings given in claim 1, are reacted withsulphur.
 11. Oxirane derivatives of the formula (II)

in which Y, Z and R have the meanings given in claim 1, except for thecompound 2-[2-(4-bromophenyl)ethyl]-2-(1-methylcyclopropyl)oxirane. 12.Oxirane derivatives of the formula (IV-a)

in which: R^(a) represents isopropyl, 1-halocyclopropyl,1-(C₁-C₄-alkyl)cyclopropyl, 1-(C₁-C₄-alkoxy)cyclopropyl or1-(C₁-C₄-alkylthio)cyclopropyl, and A represents CH or N.
 13. Oxiranederivatives of the formula (IV-b)

in which: R has the meaning given in claim 1 and A represents CH or N,where R does not represent tert-butyl if A represents CH. 14.Phenyl(oxy/thio)ketones of the formula (VI)

in which Y, Z and R have the meanings given in claim 1, where Y is not Oor CH₂ if Z is bromine.
 15. Phenyl(oxy/thio)ketones of the formula (IX)

in which X⁴ represents 5-pyrimidinyl or 3-pyridinyl and Y and Z have themeanings given in claim 1, where Z is not bromine if X⁴ is 3-pyridinyl.16. Method for controlling phytopathogenic harmful fungi, characterizedin that pyhenyl(oxy/thio)alkanol derivatives of the formula (I)according to claim 2 are applied to the phytopathogenic harmful fungi,their habitat or a combination thereof.
 17. Composition for controllingphytopathogenic harmful fungi, characterized in that it comprises atleast one of phenyl(oxy/thio)alkanol derivatives of the formula (I)according to claim 2, and an extender, a surfactant, or combinationsthereof.
 18. Process for preparing compositions for controllingphytopathogenic harmful fungi, characterized in thatphenyl(oxy/thio)alkanol derivatives of the formula (I) according toclaim 2 are mixed with an extender, a surfactant, or combinationsthereof.